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TOPICS I N INOI<(iANI(

A N D GENERAL, ( tII MIS I I < \


THE CHEMISTRY OF GOLD
A C O L L E C T I O N OF MONO(;llAl'llS 1, 1)l'I'l~1) 1iY

R. J , H. C L A K K

Department of C h e m i s t r y , Universit?, C'ollegc~L o r ~ d o ~2i 0. ( ; o r t l o t ~Slrc,c,l,


L o n d o n W C 1 H OAJ, England

MONOGRAPH l 6 RICHARD J . PUDDEPHATT


Sc~rliorLcclurcr,
I)cpczrln~cnlof Irtorgclnic, Physical ilnd Industriul Chcrnislry,
T h c University o f Liverpool.
O t h e r trlles m thc collectror~
C;roclc S t , P.O. B o x 147,
1 The Chemistry of Beryllium, by D A Everc,st ( o u t o f p r m t ) Lic~crpoolL 6 9 3 H X . Ergland
2 Inorganic Ion Exchangers, b5 (' B Amphlett ( o u t of print)
3 Introduction t o the Atomic Nucleus, by .l. G . Chninghame ( o u t of
print)
4 The Chemistry o f the Rare-Earth Elements, b y N. E. Topp (out of
print)
5 The Chemistry of Gallium, by I. A. Sheka, I. S. Chaus and T. T .
Mityureva ( o u t of print)
6 The Chemistry of Technetium and Rhenium, by R. D. Peacock ( o u t
of print)
7 The Chemistry of Selenium, Tellurium and Polonium, by K. W .
Bagnall ( o u t of print)
8 Interactions in Electrolyte Solutions, by G. H. Nancollas
9 Plasma Chemistry in Electrical Discharges, by F. K . McTaggart
1 0 The Chemistry of Niobium and Tantalum, by F. Fairhrother ( o u t
of print)
11 The Chemistry of Titanium and Vanadium, b y R. J. H. Clark
1 2 Active Carbon, by M. Smiiek and S. t e r n ? ( o u t of print)
1 3 The Chemistry of Uranium (Including Its Applications in Nuclear
Technology), by E. H. P. Cordfunke ( o u t of print)
1 4 The Chemistry of Thallium, by A. G. Lee (available from Applied
Science Publishers, Barking, England)
15 The Actinide Elements, by K. W. Bagnall ( o u t of print) ELSEVIER SCIENTIFIC PUBLISHING COMPANY
Amsterdam - Oxford - New York
(Volumes 1-15 were edited by P. L. Robinson) 1978
ELSEVIER SCIENTIFIC PUBLISHING COMPANY
3 3 5 Jan van Galenstraat
PREFACE
P.O. Box 211, Amsterdam, The Netherlands

Metallic gold has been most highly valued by man since the
Uzstributors for the United S t a t e s and Canada earliest times but, since the demise of the alchemists, the chem-
ical conlpounds of gold have not been studied as closely as
ELSEVIEH NORTH-HOLLAND INC
52, Vanderbilt Avenue those of other rare metals. This is perhaps partly due to the ease
New York, N Y. 10017 with which many gold compounds decompose hack to the
noble metal, but also due to the limited use of gold other than
as a monetary standard and for jewellery and other decorative
uses. Gold and its compounds have been regarded as the least
useful of the noble metals as catalysts, but recent progress
suggests that this situation may change significantly in the near
future. Applications of gold based on its physical and chemical
rather than its decorative properties account for a larger pro-
portion of the total gold used each year. For example, the use
of gold in micro-electronic circuits is increasing rapidly, and
thcre is increasing interest in the drtvelopment of new gold
complexes for LISV in the treatment of arthritis.
Along with this expanding use of gold, there has been an
impressive series of advances in the chemistry of gold com-
pounds. For many years, the chemistry was dominated by the
study of linear two-co-ordinate gold(1) complexes and square-
planar four-co-ordinate gold(lI1) complexes. Recently, however,
compounds of gold(1) and gold(II1) in which the metal has
higher co-ordination numbers have been studied and a new
I n c l u d e s bibliographical r e f erertces and Lndex . chemistry of gold(I1) and gold(V) has been developed. Advances
l. Gold. I. T i t l e . 11. S e r i e s .
~D181. ~9P8 ~~~~~~~~6 73-3627 have also been made in understanding the nature of compounds
ISBN o - i 4 l + - 4 1 6 2 : ~ - 2 with gold-metal bonds, and, in addition, exciting cluster com-
pounds of gold have been prepared and characterised. Organo-
O Elsevier Scientific Publishing Company, 1978
gold chemistry has seen many advances, ranging from the
All rights reserved. No part of this publication may be reproduced, synthesis of unstabilised alkylgold species like [AuMe,]- and
stored in a retrieval system or transmitted in any form or by any means, [AuMe,]; t o the preparation of carbene, alkene and alkyne
electronic, mechanical, photocopying, recording or otherwise, without complexes of gold. Many reactions are now better understood
t h e prior written permission of t h e publisher,
as a result of mechanistic studies, and structure determinations
Elsevier Scientific Publishing Company, P.O. Box 330, Amsterdam,
The Netherlands have been aided by the routine application of sophisticated
spectroscopic techniques.
Printed in The Netherlands Some of the aspects discussed above have been the subjects
vii

of excellent review articles. but. at a time when gold chemistry


is undergoing an impressive renaissance. there is a clear need for
a monograph covering all aspects of gold chemistry . It is hoped
that this book will fill this gap and that it may stimulate
Preface . . . . . . . . . . . . . . . . . . . . v
further research. for there is still a great deal t o be learned about
gold and its compounds .
R . J . Puddephatt
Chapter 1. Introduction to the Chemistry of Gold
Occurrence of gold . . . . . . . . . . . . . . 1
Gold in sea water . . . . . . . . . . . . . . . 3
Recovery and purification of gold . . . . . . . . 4
Properties of the element . . . . . . . . . . . . 5
Colloidal gold . . . . . . . . . . . . . . . . 6
Isotopes of gold . . . . . . . . . . . . . . . 7
Chemical reactivity of gold . . . . . . . . . . . 9
Oxidation states of gold and the stereochemistries of
gold complexes . . . . . . . . . . . . . . 10
Ionisation energies and electron affinities of the Group
TB elements . . . . . . . . . . . . . . . . 14
Co-ordination number in gold(1) complexes . . . . 15
Oxidation-reduction potentials . . . . . . . . . 18
Stability of gold complexes . . . . . . . . . . . 22
Theoretical studies of bonding in gold complexes . . 24
The trans-effect and trans-influence . . . . . . . . 26
References . . . . . . . . . . . . . . . . . 28

Chapter 2 . Binary Compounds of Gold


Hydrides of gold . . . . . . . . . .
Halides of gold . . . . . . . . . . .
Pseudohalides of gold . . . . . . . .
Oxides and hydroxidks of gold . . . .
Sulphides. selenides and tellurides of gold
Gold(II1) fluorosulphate and nitrate . . .
Nitrides and other Group V derivatives .
References . . . . . . . . . . . .
Chapter 3 . G o l d ( I ) C o m p l e x e s Reactions of organogold(II1) complexes . . . . . . 138
Carbene complexes of gold . . . . . . . . . . . 144
Carbonyl complexes . . . . . . . . . . . .
Alkene and alkyne complexes of gold . . . . . . . 148
Isocyanide complexes . . . . . . . . . . . .
References . . . . . . . . . . . . . . . . .151
Cyanide complexes of gold(1) . . . . . . . . .
Nitrogen donor complexes . . . . . . . . . .
Phosphorus. arsenic and antimony donor complexes C'hapter 8. C o m p o u n d s with G o l d Metal B o n d s
Complexes with gold-oxygen bonds . . . . . .
Gold-gold bonded complexes . . . . . . . . . . 157
Complexes with sulphur and selenium donor ligands
Gold cluster compounds . . . . . . . . . . . . 160
Halide complexes of gold(1) . . . . . . . . . .
Alloys and ligand-free gold-metal bonded compounds 1 6 4
References . . . . . . . . . . . . . . . .
Compounds with gold main-group-metal bonds . . . 165
Compounds with gold transition-metal bonds . . . . 169
Chapter 4 . G o l d ( I I ) Complexes References . . . . . . . . . . . . . . . . . 176
Dithiolate and related complexes of gold(I1) . . . . 70
Other stable gold(I1) complexes . . . . . . . . . 72 Chapter 9 . Reaction "Plechanisrm in Gold Chemistry
Gold(I1) complexes as reaction intermediates . . . . 74
References . . . . . . . . . . . . . . . . . 74 Ligand substitution reactions in gold(1II) complexes . 179
Substitution reactions in gold(1) complexes . . . . . 193
Electrophilic substitution reactions . . . . . . . . 194
Chapter 5. G o l d f l l l ) Complexes Homolytic substitution reactions . . . . . . . . . 200
Complexes with carbon-donorligands . . . . . . . 76 Oxidation of gold(1) complexes . . . . . . . . . 201
Nitrogen-donor complexes of gold(II1) . . . . . . 77 Reduction of gold(II1) complexes . . . . . . . . 203
Complexes with phosphorus. arsenic and antimony References . . . . . . . . . . . . . . . . . 208
donor ligands . . . . . . . . . . . . . . . 83
Nitratogold(II1) complexes . . . . . . . . . . . 85 Chapter 1 0. Spectroscopi c. Studies of Gold C o m p l e x e s
Complexes with sulphur and selenium donor ligands . 85
Complex halides of gold(II1) . . . . . . . . . . 90 Vibrational spectroscopy . . . . . . . . . . . . 210
References . . . . . . . . . . . . . . . . . 93 Nuclear magnetic resonance spectroscopy . . . . . 223
Mossbauer spectroscopy . . . . . . . . . . . . 226
Nuclear quadrupole resonance spectroscopy . . . . 234
Chapter 6 . G o l d ( V ) C o m p l e x e s Photoelectron spectroscopy . . . . . . . . . . . 234
References . . . . . . . . . . . . . . . . . 97 Ultraviolet-visible spectroscopy . . . . . . . . . 236
References . . . . . . . . . . . . . . . . . 240
Chapter 7 . Organogold C o m p l e x e s
U-Bondedorganogold(1) complexes . . . . . . . . 98 Chapter 11. Analysis and Applications of Gold C o m p l e x e s
Reactions of organogold(1) complexes . . . . . . . 109 Analytical methods for gold . . . . . . . . . . 243
U-Bonded organogold(II1) complexes . . . . . . . 1 2 1 Biological applications of gold . . . . . . . . . . 247
Catalytic properties of gold . . . . . . . . . . .253
Methods of gold coating . . . . . . . . . . . ,256
Other applications of gold . . . . . . . . . . . 257
References . . . . . . . . . . . . . . . . .257 lNTRODUCTlON TO T H E CHEMISTRY OF GOLD

Appendix
Gold-element bond lengths . . . . . . . . . . . 261 In this chapter we shall consider first the occurrence of gold
References . . . . . . . . . . . 267 and the ways used to extract and purify the element from its
ores. After this, the properties of elemental gold will be covered,
Subjectlndex . . . . . . . . . . . . . .270 followed by a preliminary survey of the oxidation states and
stereochemistri~sadopted by gold in its complexes. Finally,
some general concrpts which are useful in interpreting and
rationalising the properties of gold and its complexes will be
introduced. It is hoped that, using this general framework, the
reader will be able to place the detailed properties of individual
gold complexes, which are treated in subsequent chapters, into
their proper perspective.

OCCURRENCE O F GOLD

From studies of the solar spectrum the abundance of gold


in the sun is found t o be 0.04 parts per million (ppm), but in
the Earth's crust it is on average about 0.004 ppm. Thus, gold
is probably more abundant in the core than in the crust, where
concentration by a factor of about 1 0 3 is necessary before
economic extraction is feasible.
Concentration of gold, which usually occurs in nature in the
metallic form, has occurred in two ways. The first gives rise to
alluvial or placer gold, and consists of the weathering of auri-
ferous rocks which have been washed into river beds or similar
situations. The greater specific gravity of gold (19.3) compared
with residual rock (- 2.7) leads to gold settling out while lighter
rocks are washed away. Alluvial gold, once discovered, is often
easy to extract as nuggets or grains by simple gravity concentra-
tion and the sources which gave rise t o the great gold-rushes
of California in 1848, Australia in 1850 and the Yukon in
1 8 9 6 were of this form. Much of the gold found in the lJral Dissolution and redeposit~onof gold in stream beds may
mountains of the t1.S.S.R 1s also alluvial gold ilso be responsible for the formation of large crystals of allu-
The greatest gold fields are those in South Africa, where the L ial gold. Particularly mteresting is the observation t h a t some

gold o w u r s as thin veins in quartz rocks. Thc gold, known as micro-organisms and then- metabolites isolated from gold-
vein or reef gold, IS present as micmscopic part~clesso that learmg deposits are capable of dissolving gold. The maxlmum
extraction is considerably more d~fficultthan for alluvial gold. i~ssolutionof gold by isolated bacterial metabolltes studied
In general reef gold 1s found In quart^ o r a l h ~ t rocks,
t often W far is 10-35 g m - ' in 20 days. Ilissolution is aided by t h e
along with irotl pyrites D t q ~ ) s ~wltht s silvt)r and other rare ,)resence of aspartic acid, histidinc, serinc, a l a n ~ n eand glycine
metals often o w u r in volcanic rclgions c.ontrollcd by nialor fault ind by metal oxidants [ 3 ] .
zones. Itere, cSoncentratlonof the gold takes place hy hydro- The only compounds of gold which form important minerals
thermal metamorphism frvrn bas~crocks dtid tlryosition ln .m the tellur1dt.s. Examples include calavwite and krrnnerlte,
s t d ~ n ~ c n t a rorks
ry 11 2 1 (;old :s ( onsidtrtvl to hr) an mcrt wh1c.h are dlffcrent crystalline forms of AuTc?, m o n t h r a y ~ t e ,
n~c$al but ~t (,an bv d~ssolvcdyuitr rc~atlllq halld(1 or >ull)hidtl ,,
Zuzrre and m ~ r e dg o l d - s ~ l v ~tellurides
r such as sylvanite,
~ o n in
s the presence of ouidlslng agents to g i v ~gold(if1) or \uAgrI'e, Nat~vc.gold also contains sllver m varying propor-
goid(1) conlpleut~s.It 1s prohal-)ly in thli way that gold is dis- tlons, one well-knowt~rxamplv hcmg clcctrum with about
solved when hot volcanic rock 15 hurled o r when a h o t granitt. 20% silvcr. Uther v a l u a b l ~txlcmcnts obtained as m m o r constl-
rntrusion riws n f w t o t h iurfarr
~ of thc Fhrth's crust Stud1r.s t ~ ~ c nfrom
t s gold ortls a t . ~ridlum,osmium, platinum, rhodium,
of model systt.m~suggest that i f the oxygen rani-clntration is ruthenium and palladium as wrlll as cwppr3rand nlckel.
governed tly t h tlqu~hhrium
~ The gold fields o f South 11 fr1c.a h a w so far y lelded over 3 1
million kg of gold, wh1c.h is m o w than half thc gold reserves
of the world. The second largest producer is the U.S.S.K. but
the precise amounts mined thew are not put)l~shtd.No other
and the chloride concentration and pH by the mica feldspar
quartz buffer system, then a t the high pressures and tempera- country produces comparable q u a n t l t ~ e sof gold, b u t Canada,
tures o f 400-600 "C which are likely, gold would dissolve ulu thc U.S.A., Australia and othcr African and South Amcrican
reactions of the typtx: countries still product, significant amounts.

As the solution cools t o 300--400 "C the concentrations o f


oxygen and o f HC1 are expected to decrease sharply, and gold The presence of dissolved gold in sea water was discovered In
is redepcsited. The nature of the deposit will obviously depend 1872, and many uniformly unsuccessful attcmpts have been
o n t h e precise conditions, and o n the nature of the convection made t o recover thc gold cornmcrcially. The most famous
patterns or percolation routes of the cooling solutions. Hydro- attempt was made by Fritz [laber, with the intention of paying
thermal transfer of gold as the complex ion [Au(SH), ] - may off the German war debt, in the years 1920-1927. The method
occur in some cases [ 2 b ] . was based o n reduction t o metallic gold using sodium poly-
sulphide, but the available estimates of the gold concentration
* There is n o direct evidence for the existence of H3AuCI,. H[AuC14] is in sea water were t o o high by a factor of about 1 0 3 and t h e
perhaps more likely. results were all disappointing. Most other methods rely o n
adsorption o f gold on various media, including rc.c.cntly poiy The solution is filtered t o remove the gangue and the gold is
mers contaming t h ~ o groups l which coniplm strongly to go11-1, rcprecipitated with zinc:
Some of these methods are useful in concentrating gold, so that
accurate analyses can be pcrformc.d, and ~t is now thought that
the concentratlon of gold In sea water 1s about 2 x 10 " 11, Recovery of gold w ~ t han efficiency of around 98% can be
though the c~oncentrationfluctuates dcpenc-ling on t h e gro ~ c h i t v e dusing thls combined method, with the product from
graphic region and depth from w h ~ c hsamples arc6iwll~cttct the fmal s m e l t ~ n gprocess containing 88-90% gold. The resi-
15. 61 I t thcsc low c*onccntration~, ~t is not possiblt. t o d t t w dual constituents are silver (-10%) and small amounts of copper,
mine clirt.ctly t h c nature of the gold spcc~csp r r v n t , hut c.,ilc,~la- lead, zinc, Iron and platinum group metals.
tlons hastd o n redox potent~alsof gold compounds dnd t h ~ Most gold IS p u r ~ f l e dby t h e chlorination process. Chlorine
t w n ~ p o s ~ t i oo nf sc.a water suggvst that tho gold( l ) c~)mpltt\cIon gas is bubbled through the moltcn gold and t h ~ converts s
l i~rtbd~)riltl~~itt'n.with bnl,~llt,r, m o u n t \ o f I \uC'IRr 1 ,ilv(lr and haw mc>talst o t h t chlorides which float t o the surface
m d c~thorI)rorno, loci0 ,ind tiytlroxo c.otr~~)lc~\ ~ ( I I of
I ~ gold(l) nnd can be removcd r a s ~ l y Gold . o f purity 99.5% 1s produced
17 1 nlso hc>~ng prtwnt In this way and, ~f n c ~ ~ s s a r 1s y ,further rcflned by elt~ctrolysls.
I'he anode is thc crudcl gold, the r.lec.trolyte IS kI[AuCI41 in
hydrorhlor~cacid, and the cathode is pure gold. Pure gold is
dcpositcd a t t h e cathodc, whdc platmum and pallad~umcan
Rt~covcrqof gold from ,illuv~aldtyoslts by gravity conc cwtra- 1)e rccovc3red from the anodcx mud.
tion dates bach a t lcast 6,000 yc1~lr\ I'hc g o i d - c ~ ) n t a ~ n matcw;il
~ng A convenient method for the recovery of gold from gold
was c*cinvcqrd watcbr d o w n , I \11i1( P ( q u ~ p p rwith
~ l transvcrw rc.slducs In the laboratory consists of pyrolysis of the r w d u c q
r~ffleswhlch trapped the heavier gold particles. It 1s thought followtad by dissolution o f the gold In nquu rr.gla. The pII IS
that the use of animal hldes in this prowss gave rlse t o the Iegtwd adjusted t o p11 2-4 by addmg s o l d sodium h y d r o x ~ d and t the
of the Goldcn F l t w ~of Jason and the .Irgonauts. A11 Improve- gold is reprcclpltated uslng sodium s u l p h ~ t eas reducing agent.
mrbnt to the. method was dwt~1o~)r.d wh1c.h ~nvolvcdthe use of 12 slmllar procwlure can bt. uscd t o obtam gold powder from
mrxrc,liryIn tht. nfflrs t o amalgamatil the stttling gold partlclc~s, m&ssivc>gold.
the gold kwing re( ovcrrd by distilling off the rnc3rc.uryin retorts
and thc gold f~nallysmt>ltrtl
'I'hesr. mcthods arc. u n w ~ t a h l tfor
~ h ~ g hyic'ld rccwvery of
reef gold in wh~c-hthe gold con(-entratlon may hc only 1 0 ppm
o r less, and the Following is a typical modcrn procedure. The Gold is perhaps the most bwutiful of thp chemical elements
ore 1s first crushed and then mllled t o give the fine particles and has been known and treasured by man sincc t h e earliest
needed for efficient extraction. Part o f the gold 1s still recovcrcd times. In the massive form it is a soft, yellow mctal with the
by the gravity concentratlon, amalgamation, retortmg and highest ductility and malli~abilityof any element; thus one
smeltmg procedures whlch have been much ~ m p r o v e dby modern ounce of gold can be beaten o u t t o 300 square feet. Gold has
technology. The tailings from this process are not discarded an atomic weight of 196.967 and a density a t 2 0 OC of 1 9 . 3 2 g
however, b u t are treated with a l k a l ~cyanlde and compressed cm-'; the pure metal melts a t 1 0 6 3 "C and boils a t 2966 "C. T h e
air t o dissolve the gold according t o the equation: beauty and rarity of gold has led t o its use in jewellery and in
coinage and as a standard for monetary systems throughout
the world. Since gold is such a soft metal, it IS usually alloyed solution of gold in aqua regia with ethereal oils. Formaldehyde
t o give it more strength. In thesr alloys the term carat is used and hydrazine hydrate are now commonly used as reducing
to express the amount of gold present, 24 carats benlg pure agents. Particularly important is the "purple of Cassius" which
gold. Alloys of gold with the other elemcnts of group I B are has long been used as a colouring agent for enamel and glass.
most frequently used. Thus, colnage gold typ~callycontains This is thought t o be a mixed colloid of hydrated tin(1V) oxide
10% copper, while gold used in jewellery and dent~strymay and gold formed by reducing [AuCl,]- with tin(I1) chloride.
contain varylng proport~onsof silver and copper. The colours .2 purple or ruby-red precipitate is formed on heating the solu-
of the alloys are frequently controlled by the other metal. tion. This forms the basis of a sensitive test for gold; thus, the
Thus, an alloy c-ontalning 50'4 copper is dark red, and one purple colour is formed if a 10-8 M solution of [AuCl,]- is
conta~ning65% s~lvcris w h ~ t xand hardly d~stinguishableto added to a saturated solution of tin(I1) chloride.
tht, i5yt>from pure s~lvcr.Thcb whlti, gold cornrnotily used In
jcwtlllcry contains 75--85S gold, w t h 8 10r; nnlckt.1 and !SOTOPES O F GOLD
2 9": ~ m cw, h ~ l enorcl cxpt\nsivt1whlte alloys art1pallad~urn Gold has an atonuc number of 79 and an atomic weight of
gold (90% Au, 10% Pd) and platlnurn- gold (60% A u , 40% Pt). 196.967. Thus, the nucleus of the only stable isotope I 9 ' ~ u
Gold also has h ~ g hthern~aland i.l(vtr~calconductiv~ty;hence contains 79 protons and 1 1 8 neutrons. Details of the other
its use In electron~cs.The high cost of gold necess~tatrsthe use known isotopes of gold are given in Table 1.1.
of very thm films, f o r m d by c.lrc.troplating o n a base metal The neutron-deficient isotopes are prepared by bombarding
support, for gold switc.hmg dcviccs lighter atoms with positively charged particles in a cyclotron or
Like the>other group [B clemrnts, gold crystallises in thc linear accelerator The ~sotopesof mass numbers from 1 7 7 t o
face-ccntrcd cubic lattice. and the closest iritcr-nuclt.ar d~stance 183 are all alpha emitters and all have half-lives of less than one
is 288.4 pm. rnmute, while those with mass numbers of 185-196 decay by
At high temperature in the gas phase, gold exists as a mixture electron capture accompanied by gamma radiation and in some
of atoms and dmtomic molecules. The d~ssoc~ation energy cases by positron emission. Of these isotopes the only long-
( D o " )of tlu, is 2 2 1 + 2 kJ mol-'and the . \ U -Au bond length lived one is ""Au with a half-life of 1 8 3 days; this isotope is
is 250 pm 1101. prepared by the rrac'tion.
' ; ' ; ~ t+ ; p - ':;;.\U + ;)l,
COLLOIDAL CiOLL) A target of platinum (which in natural abundance contains
33.8% """t) is bombarded with 22 MeV protons in a cyclotron.
Solutions containing gold complexes such as [AuCl,] are This is an exptwsive process made yet costlier by the need for
easily reduced to gold, and under controlled conditions coll- subsequent sclparation of gold from platinum; hence '"AU is
oidal gold may be formed. Colloids of gold may be red, blue not widely ustvi.
or violet depending on the mean particle size and shape and The neutron-heavy isotopes are prepared by neutron capture
have been known for a long time, certainly since the 18th reactions, and all decay by p-emission accompanied by gamma
century. Various reducing agents can be used for preparing radiation. The most important isotope in this group is I o s ~ u ,
colloidal gold, some of the earliest being tannin and phosphorus, which is prepared in a nuclear reactor by the reaction:
while the "potable gold" of the alchemists, t o which fabulous
medicinal powers were attributed, was obtained by reducing a ';:Au + An + Au
This is a particularly favourable reaction since 1 9 7 ~ the
u,
TABLE l . la only naturally occurring isotope, has a high neutron capture
cross-section of 98.8 barns. Thus, with a moderate neutron
The Isotopes of Gold
- flux of 2 X 1013 n cm-* S-', a specific activity of 1 curie per
Mass No h Half life Vode of decayC gram is obtained in 6.5 hours. The isotope '"AU is widely
---
lsed in radiotherapy, in medical diagnosis and for tracer
177 135s Q ,tudies.
178 2.65 s Q
179 7 25s Q
181 11 5 5 c U, EC CtIEhIICAI, REACTIVITY O F GOLD
183 25 5 S N
(;old is the most noble of the metals, being the only one
185 4 3 rnln a , EC
186 12 m111 l?<', y
which is not attacked hy either oxygen or sulphur a t any temp-
187 X mln cr, KC erature. Gold does howtwx react with tellurium at high tempera-
188 8 mm EC, y turcs, to give AuTc,, and reacts with all the halogens. Of these,
189 29 7 mm E(', y hrorninc. is the most reactive and reacts exothermally with gold
189m 17 mln EC, y powder at room tempcmture t o give Au,Br,. The reaction with
190 39 min EC, y ci~lorinchas been studied in more detail due to its application
191 32 h E(', y
192 5 0 h E(:> 0 +, 7 in thr. purification of gold. At temperatures below 130 "C,
193m 395 Y chlorine is adsorbed onto the surface and then forms surface
193 17 5 h KC', y conlpou~ds;at temperat~1rc.sbetween 130-200 "C, further
194 39 5 h E(',p+, 7 :cmtion can take place but the rate is limited by the rate of
195m 31 0 s p+> Y Jiffusion of chlorine through the surface layer of gold chlorides.
195 1 8 3 day EC, y
196m 97h '7
i ) ~ l above
y 200 "C is a high reaction rate achieved as the gold
196 6.2 day EC, /j, Y chlorides then sublime, thus continually exposing a clean gold
197m 75s Y surfacc. [ 111.
197 hLdble
(;old will dissolve in aqueous solutions containing a good
Izgand for gold and an oxidising agent, but neither condition
198 2 70 day it Y alone is sufficient. Thus, gold will not dissolve appreciably in
199 3 1 5 day 0, Y
200 48 4 miri 8, r hydrochloric or nitric acid, hut dissolves readily in aqua regia
201 26 min 0, Y t o give t,ctrac:hloroauric(III)acid, H[AuCl,]. Similarly, gold
202 30 S 0.y ill dissolve in hydrochloric acid in the presence of hypochlo-
203 55 S 0, r r'lte or iron(ll1) as oxidant. The dissolution of gold in cyanide
204
-
4 05 S B, r -01utions with air or hydrogen peroxide as oxidant is another
a F r o m : L. Myerscough, Gold B u l l , 6 ( 1 9 7 3 ) 6 2 m = metastablc. example of this effect. The reaction with oxygen as oxidising
C a = alpha emission, EC = electron capture, P+ = positron emiss~on, agent apparently takes place by adsorption of oxygen onto
B = beta particle emission, y = gamma r a d i a t ~ o n . the gold surface, followed by reaction of this surface layer
with cyanide t o give first AuCN and then the complex
[Au(CN),]- which passes into solution.
Atomic gold is considerably more reactive than the massive very low solubility (e.g., AuI) or strongly complexed (e.g.
metal. Reactions of atomlc gold can be carried out by evapora- [Au(CN),]-) according to the equations:
tion of the metal at high temperature under vacuum and then 2Cu(I) + Cu + Cu(I1)
co-condensing the gold vapour with a suitable reagent onto an
inert noble-gas matrix at liquld helium temperature. In this way 3Au(I) + 2Au + Au(lI1)
the complexes mono-(dloxygm)gold,A u ( 0 2 ) ,and tnono(ethy- Since Au' has the closed shell electronic configuration [Xe]
lene)gold, Au(C2hI,), and the carbonyls Au(CO) and Au(CO), 4fI45d", gold(1) complexes are diamagnetic and adopt regular
can be prepared and ~dentlfledspectroscoplcally. Co-rondensa- structures. The most common stereochemistry is linear, the
tion of atomic gold with carbon monox~deand dloxygen qves co-ordination number of the gold atom being two [12-141,and
the complex such complexes may be cationic such as [Au(PPh,),]+, neutral
such as [Au(CN)(PPh,)] or anionic such as [AuCl,]: In this
respect gold(1) differs from silver(1) and copper(1) which have
a greater tendency t o form complexes with higher CO-ordina-
tion numbers. Thus, the complex MI(PEt,) is monomeric when
M = Au, but exists as a tetrarner [ { MI(PEt,)},] with bridging
iodide ligands when M = Cu or Ag, so that the metal atoms have
whlch 1s thought to be involved in the gold-catalystd rcactlon co-ordination number four. Higher co-ordination numbers are
of CO and 0; to give CO,. ,411 these gold compounds dec-om- also known for gold(1). Thus, trigonal planar complexes [12,
pose on warming the matrix [ll b 1. 151 wlth co-ordination number three such as [Au(PPh,),]+ and
[AuCl(PPh,),], and tetrahedral complexes [l61 with co-ordina-
tion number four such as [Au(PMc,),Jt are known but these
OXIDATION STATES O F GOLD AND THE STEREOCHEMISrrRIES
readily lose phosphine ligands and revert t o the more favoured
O F GOLD COMPLEXES
linear two co-ordinate form. We shall consider later in this
In complexes containing a single gold atom, the oxidation chapter possible explanations for this relative preference of
states I, 11, I11 anu V are well established and gold also forms gold(1) for co-ordination number two when compared with
many complexes with metal--metal bonds in which it is diffi- copper(1) and silver(I), and the similar effect observed in group
cult t o assign formal oxidation states to the metal atom. Gold IIB, where mcrcury(I1) forms many linear two co-ordinate
has the electronic configuration [Xe] 4fi45d"6s' and compounds but zinc(I1) and cadmium(I1) d o not.
belongs t o group IR af the periodic table along with copper and
silver. In this section, we shall study briefly the nature of typical ( b ) Oxidation state II
complexes of gold in each oxidation state so that comparisons
with the other group IB elements can be made, and a detailed The oxidation state two is dominant in the chemistry of
treatment will be found in subsequent chapters. copper, but considerably less common for silver and very rare
for gold. Thus this oxidation state is established for gold only
(a) Oxidation state 1 in the following situations:

Of the group IB elements, silver alone forms a simple aquo (1) There is strong evidence that gold(I1) species are formed
ion in oxidation state I. Gold(1) and copper(1) compounds as transient intermediates in redox reactions between the stable
disproportionate in aqueous solution unless they are either of oxidation states I and I11 [17].
[Au(OH,),] " is never formed even on dissolution of gold(II1)
hydroxide in nitric acid or sulphuric acid [20]. Five co-ordinate
gold(II1) complexes are rare, but when formed they are square
pyramidal or distorted square pyramidal, as in [AuC1,(2,2'-
:,iquinolyl)] and [AuCl, (2,9-dimethyl-l, l 0-phenanthroline)]
vvith rigid bidentate nitrogen-donor ligands [21]. There is
~videncethat the complex ion [Au(diars),I] ,+,where diars =
1.2-his-(dimethylarsino)benzene,is five co-ordinate but its
,tructure is unknown. Trigonal hipyramidal gold(II1) complexes
ire generally invoked as intermediates during ligand substitu-
8 ion rrwkions In square planar gold(II1) complexes. In co-ordi-
dtion number six, a tetragonal stcreochemistry is always
( 2 ) Stable gold(lll zpt>cit.s may be l o r r n ~ d111 wh1c.h t h t w is
~ssumt.d[22] and has been proved for [Au(diars),I,]'. The
a gold- gold bond .An c~xan~plt~ is g1vt.11in Fig. 1 1 ( 18 1.
-1tuatlon may be comparcd wlth that for [ c u F , I 3 and [AgF,13
( 3 ) With certam un5atr1r;itc~isulphur-donor I~gandsSLI( h as
wh1c.h are paramagnetic w ~ t hp c , , 2.8 B.M. and 2.6 B.M.,
maleo11itrlled1thioli1te 1011, milt' , sola able cwrnplc\t.s of gold( 1 1 )
wspectively, at room tempcraturc; these coniplex ions presum-
such as [ A u ( n ~ n t ) ~ with
] a square planar four cw-ord~nate
ihly have regular octahtdral structures. Howcvvr, all other
gold(I1) centre as shown below may he fornitd.
( ' ~ ( 1 1 1 and
) Xg( 111 on~poundhare diamagnt3tic. with square
&mar co-ord~nat ion

* d ) Oxidation state V

'I'hc first gold(V) complex containing the ion [AuFJ was


In gold(I1) complexes the metal has the 5d" configuration and reported in 1972 by Bartlett and co-workers. It is diamagnetic
such complexes are expectcd to he paramagnetic unless thcw and has a regular octahedral structure with the low spin 5d6
IS a gold-gold bond. Monomeric gold(1I) compltxes w ~ t h electronic configuration [ 2 3 ] . The compound AuF, can also
dith~olateand dith~ocarbamatel~gandsappear t o bc ,tabiliscd be prepared. These compounds are very powerful oxidising
by delocalisation of the unpaired clwtron over the unsaturated agents, and no analogous compounds of copper and silver are
ligand [19]. known.
From the foregoing account, it will be clear that there are
( c ) Oxidation state I l l more differences than similarities between the properties of
gold compounds on the one hand, and of either copper or
This is an important oxidation state for gold but is rare for silver compounds on the other hand. In many cases, it is more
copper and silver. All known gold(II1) complexes are diamag- valuable t o make horizontal comparisons of gold with the
netic with the low-spin 5dHelectron configuration, and the neighbouring elements platinum and mercury in the periodic
vast majority of these compounds have the four co-ordinate table than with the other group IB elements. Thus, isoelectronic
square-planar stereochemistry. Examples include the complex species such as [AuC12]- and [HgCl,], [Au(PPh,),]+ and
ions [AuC14]- and [Au(NH,),] 3', but the simple aquo ion [Pt(PPh,),], and [AuCl,]- and [PtC1,I2- exist. In the following
sections we shall attempt to rational~sesome of the similarities from the nuclear charge by both the 4f and 5d electrons, so
and differences between gold and the other group IB elements, that it feels a high effective nuclear charge. It is a combination
and to study the factors which affect the relative stability of of this high ionisation energy and the high binding energy
the common oxidation states ( I ) and (111) in gold complexes. which gives gold its noble character.
Variations in the second and third ionisation energies are
also noteworthy. Thus, the relatively high second ionisation
IONISATION ENERGIES AND ELECTRON AFFINITIES O F TIIE energy for silver accounts partly for the dominance of the + I
GROUP IB ELEMENTS oxidation state for this element, and the relatively low third
ionisation energy for gold leads t o the + I11 oxidation state
The factors governing the stability of oxidation states of an being preferred. Subsequent ionisation energies are also lowest
element are of course complex, and cons~drratlono f cornplcte for gold, no doubt explaining the existence of the + V oxida-
energy cycles 1s desirable. Ilowever, Lhc required data are ~ i o t tion state for gold b u t not for silver or copper.
available for many compoulids, so that we are driven to use Accurate valur.s of the clcctron affinities of the group IB
criteria such as lonlsation enthrglcsand electron affinltles as a clrments are difficult to obtain, but there is general agreement
general guide. These are given In Tablc 1 2 and are particularly that gold has the highest value. Values of 226 and 270 k J mol-'
useful for the group IB elements. have bcen proposctl by different workers 123, 241. These
rrbtivdy high va1uc.s have promptr.d the suggestion that gold
TABLE l . 2 may he considcwct as a pseudohalogen [cf., E.A. for iodine is
296 kJ mol-'1 and there is indeed evidence that the compound
CsAu may be cwnsidrwd to be CS' Au-. Certainly gold is
Element 1st 2 nd 3rd 4th expected t o have a high electronegativity on the basis of its
high ionisation ttncrgy and electron affinity.

CO-ORDINATION NUMBER IN (;OI,Il(I) COMPLEXES

As mentioned c a r l ~ ~gold(1)
r, complexes have linear two co-
It is worth noting that the first ionisation energies are con- ordinate stcreochemistry much more commonly than copper(1)
siderably higher than for the alkali metals (e.g., K, 419 kJ mol ' ) or silver(1) complexes. Thrre has been some debate about
The ionisation process for potassium is K { [Ar] 4s' l + whether copper(1) or silver(1) has the greater tendency t o linear
K+ {[Ar] 1, while for copper it is Cu {[Ar] 3d"4s1 1 -t co-ordination, and this may be dependent on the ligand t o some
Cu' {[Ar] 3dI0}. The outer 4s electron feels a higher effective extent. The tendency to form linear complexes can be measured
nuclear charge in copper than in potassium because the increasrd by the relative magnitudes of the second and third stability
nuclear charge in copper is not balanced due to the poor shield- constants. Thus, for the cyanide complexes the ratio of log P,/
ing by the electrons in the diffuse 3d" subshell. The first log P, is for Cu(1) 1.25, for Ag(1) 1.11 and for Au(1) 1.00, so
ionisation energy for silver is lower than that of copper due that in this case the tendency to linear complex formation is
primarily to its greater atomic radius, but there is a large Au(1) > Ag(1) > Cu(1). The factors responsible for this sequ-
increase for that of gold whose electronic configuration is ence are not clearly understood and several theories have been
[Xe] 4f'45d106s1.Here, the outer 6s-electron is poorly shielded put forward.
Firstly, it can be said that steric factors are unlikely to be the p-orbitals of copper and silver, which are at relatively low
Important when considering two- and three-co-ordinate com- imergies.
plexes, so that electronic factors must be responsible. Consider- A third theory is based on the Ligand Field theory of bond-
mg only smple electrostatic effects, a metal ion with a high ing [27, 281. Thus, in a linear complex with the ligands lying
polarising power should have a high co-ordination number. dong the z-axis, it may be favourable t o hybridise the filled
Thus, for the group IB metals in oxidation state I, the order td,z and vacant ( r l + 1 ) s orbitals. This will give one orbital
should be dependent on the ionlc r a t h wh~chare C'u' 81 pm,
.?\gt 126 pm and Au' 137 pm This g~vrsthe mrrect serles,
b u t would wrongly p)rcti~c,t3 c4owr iirn1lar1t-yof sdvw to gold
rather than to cwpper
'2 sec oild t,htwry curisrdi.rs t h e n,it u r t ~o t t h(, o r b ~ t d su s ~ i
:.l t)ordi:ig I'hus ,p 11) h i d j r h i t d , will I N i t ~ 111 d 11ne,u

Fig. 1 . 2 . f I y b r i d i s a t ~ o nsrhrmc* I'or goltl(1)

complrxc~s,sp2 hybrid orbitals in trigonal planar complexes


and sp3 hybrid orbitals in tetrahedral complexes. The ease with
which hybridisation of s and p orbitals takes place will depend ' ' 1 ~ . 1 . 3 . tIy1,ridisation o f :)d,2, 6 s a n d 6 p o r t ~ i t a l s (
. a) formation of
on the energy separation between these levels. This is illustrated ,
*iyl,rid orbitals $ a n d I)] rtnmoving r ~ l c c l r o ~ density
i i n t o $ away f r o m
!Ire ---axis, ( h ) formation of linear bonding hybrid orbitals f r o m $ 2 and
in Fig. 1.2. . E. Huheey, Ir~orgclrr~c.
'<pi o r l ~ i l a l s (J. ('hc~~rllslry, Harper a n d R o w ,
The rzs-tzp separations for Cu, Ag and Au atoms are 3.79, i,ondon, 1975, p. 372).
3.66 and 4.63 eV, respectively. Thus sp hybridisation rather
thar, sp2 01. sp3 hybridisation is expected to be more favour- w ~ t hmaximum electronic density in the xy plane and one with
able for gold than for copper or silver, since the higher s-p maximum electronic density along the z-axis as illustrated in
separation will make hybridisation of s and p orbitals more Fig. 1.3.
difficult [26]. The same conclusion is reached if the bonding Now, if the electron pair is in +,
rather than the d12 orbital,
is considered in terms of Molecular Orbital rather than Valence there will be less repulsion between the electron pair and the
Bond theory since the p orbitals of gold are at relatively high ligands, and the complex will be stabilised. This is a second-
energy, and therefore less likely to take part in bonding than order ligand field stabilisation energy. The orbital $, will
hybridise with the (n + 1 ) p orbital t o form two linear hybrid where .rr" is the standard electrode potential (estimated [25]
orbitals to overlap with the ligand orbitals and so give a linear to be +1.7 V though a value of 1 . 8 3 V has also been suggested
complex. This d s mixing will again become less favourable as [29]). This then reduces to (IT in units of volts):
the d--S separation increases. The energies of the lowest d9s
state above the d i Oground state are for Cu' 21,928 cm-',
.rr = 1.7 + 0.059 log,, [Au' l
Ag' 39,164 cm-' and Au' 15,039 cm-'. Thus, the second- It is possible t o derive similar expressions for alternative
order ligand-field stabilisation energy on formation of linear oxidation processes [30] :
complexes is expected to follow the series Au' > Cu' > Ag'. Au -t i4u3+ + 3e; .rr = 1.50 + 0.0197 log,, [AU"]
Thus, again gold(1) is correctly predicted to have the greatest
preference for linear co-ordination, but the prediction that
copper(1) should resc.mblt~gold(1) more than silver(1) is not
upheld.
The predictions of the three theories can bc sun~marised These reactions can only take place if sufficiently strong
in terms of the ttlndency to form linear cwmplexes: oxidants are prtwnt, and reactions in aqueous solution are
(1) Polarising power of M ' predicts Au(l) > Ag(1) 3 Cu(l) further limited by t h e limits of stability of water to oxidation
( 2 ) s-p energy separation predicts Au(1) 9 C:u(I) > Ag(1) to oxygen, or reduction to hydrogen.
( 3 ) d- s energy sepearationpredicts A u ( l ) > Cu(I) 9Ag(1) The system can hc cxrwssed graphically in the Pourbaix
diagram in w h ~ c hthe cc~u~librlum potential of each couple 1s
Thus, if all threr. effects are apprcciablc, a combinetl predic-
-
tion Au(1) S Ag(1) Cu(1) m ~ g h be t deduced, in agreement
with experiment. It is, however, difficult to estimate the wla-
tive importance of the three c.ontributions.

OXIDATION-REDUCTION POTENTIALS

( a ) The aqueous chemistry o f gold


OH
To understand the nobility of gold, it is useful to consider
the redox potentials of gold in the absence of co-ordinating 0
U --_
04
ligands. Thus, for gold to react it must be oxidised, e.g., 8 AU

Au'(aq) + e-
Au
--a-..
L
+
04
The tendency for this reaction t o take place is given by the ..._
Nernst equation: 0 2 4 6 8 pH
1 0 1 2

RT Fig. 1 . 4 . Pourbaix diagram for the system Au-H20 at 25 'C. The


.rr = .rr" + 2.303 - log,, [Au+]/[Au] concentrations of all gold species are 1 0 - M.
~
F
plotted against pH for particular concentrations. A simplified Thus, In the presence of a good ligand L for gold(I), a high
Pourbaix diagram for gold (using a concLentrationof M) value of K and a low value of (T* )' will be obtained. Some
is shown in Fig. 1.4 and indicates the conditions under which typical standard potentials are given in Table 1 . 3 [25, 29-34].
particular species are expected to be formed [311. The mean- Values corresponding to equation (S) are termed T,: to indi-
ing o f the diagram becomes clear, once it is realised that the cate that they refer to oxidation of Au(0) to Au(1). The order
dotted lines ( S ) and ( 2 ) represent the lim~tso f stability of ,,
of decreasing TT is then the order of increasing stability of
water Now the o\idistd forms of gvld cxlst only at potentials the compl~xes[AuL,]'. Note in particular, the low value of
greater than for line (1). lTnderthew cond~tions,water will ,,
TT for oxidation of gold in the presence of cyanide. It is this
be oxldised to o x y g ~ nand thc~v a r i o ~ ~oxidised s gold species case of oxidation of gold in the presence of cyanide which
will he reduced to gold metal. l'hus, In the absence of 00-ordinat- makes the cyanide process for the extraction of gold feasible.
~ng Ilgands, gold cannot i-,r o\iltl~ardb y ihssolvtd oxyge~lm
ihe presenc't. o f t,!thitr ~ t r l , r ~.icg~ d ~s ), trr # ) n g a l k , h (;old i s
h.only rni>t,~lfor whlc h thls 1 5 tht. abcl. .urd i i 11.111, tr~11)tht,
S t a n d a r d r t d o x potclnti;ils(V) I'or g o l d in a q u e o u s solut.ion
most noble o f t hc mctall~celcmcwts
-. **
1,ig;ind . n1.0 11.0 n.3. I

fI20 + 1.7 + 1.50 t- 1.4


The wason for the high electrode puttwtials for vxidation (+2.12)
of gold in the :ibsenw o f ( omple\ing Iigands 1it.s i n the vwy Cl +l.l5 + 1.00 + 0.93
low ,tahilit> o f ihc~~ l y u u~ c r l i s[,4u(OH, ),l and [.Zu(OH, ), I I f
+
Br + O 9G + 0.8 6 + 0.8 1
I + 0.5 f; + 0.5 7 + 0.57
The potentials are lower in the presence of complexing ligands. ~

S(:N- +0.67 +O.G +0.62


Thus c-onsider the equilibrium in the prcsclnce of a ligand I,. NI-1 t0.563 +0.325 +0.206
thiourra C0.38
selenourea + 0.20
CN- 0.61
Sul~stitut~ng
111 thc. Nernst cquatlon uscd prcuously the
cyuillbr~umc'oncentrat~onfor [Xu(OH,),1' i n the prPsrnw
of chlor~de,we find. I t should be realised, however, that the standard pottsnt~nls
only tell us that the rractlon is feasible thermodynamically.
Whether it takes place readily or not, wlll depend on kinetic
factors.
I t is, of coursc, possihlc to oxidise gold to gold(111) in the
presence of suitable ligands :

Again, the standard potentials nz, will depend on the stability


where (T-)l is the standard electrode potential for the couple:
constant for formation of the complex [ A U L ~ ] ~Typical
'. values
Au + 2L [AuL,]' + e- (1) are given in Table 1.3.
hard and soft ligands so t h a t gold(1) may be considered t o be
the softer metal ion*. Copper(1) and silver(1) are also soft
acids and, ~ n d e e d there
, IS a linear correlat~onbetween
any two of logo, for [AuX2]-, [AgX,]- and [CuX,]-, where
o2 are the s t a b h t y constants for different ligands X. Again,
gold(1) discrimmates more than copper(1) or silver(1) between
the ligands. T h ~ is,s of course, tn agreement with the general
predictmn that largr metal tons In low oxidation states w ~ l l
have the greatest "class In" o r soft character.
Stabll~tyconstants for gold(1) 111 aqueous solution are
difficult to obtilin duo to the tendrncy t o disproportionate,
and more. e ~ t c ~ n ~datat v o h a w h w n obtained [ 36, 371 for
ac.tton~trtlcs o l u l ~ o n shy s t ~ i d y ~ nthv
g qi1111br1a

Ph,PO iMt.,S K py S< AsI'h , < NII, < Pt'h, - MeNC

Again, the data show quite clearly that gold(1) is a "class b"
From the forego~ngdisc*ussion. it will br. clear that both metal ion. This is confirmed by studying complexes of gold
gold(1) and gold(II1) form m o w stablv complcxcs w ~ t hI than with ambidentatc ligands, in which both gold(1) and gold(II1)
with BY, and with Hr- than w ~ t h('l . Thus, In both common a l n ~ o s invariably
i b o l d t o the solter end of the ligarid [38].
oxidation states gold 1s a "class h" metal or a "soft a d , "
preferring t o bond t o large polarisable ligands. LVe have also * However, evidence that gold(II1) is a softer acid than gold(1) has been
seen that gold(1) d ~ s c r ~ n ~ i n amore
t e s than gold(II1) between presented recently [29 1.
Thus, complexes with NCO- ligand are N-bonded rather than TABLE 1.4
0-bonded, with NCS- they are S- rather than N-bonded, and
Orbital population and atomic charges in the complexes [AuX4 ]-and [AuX2] -
with thiosulphate or sulphite they are S- rather than 0-bonded.
In certain cases, thiocyanate complexes of gold(1) have been
shown to contain a small proportion of the N-bonded isomer
in equilibrium with the S-bonded form [39]. The amount of
this N-bonded form in the complexes LAuNCS increases with
the trans-effect of L, decreasing in the order L = P(OPh), >
PMe, > PPh, > AsPh, > S(CH,Ph),. This is an example of
anti-symbiosis, in which a soft ligand bound to a "class b"
metal destabilises the bond between the metal and another
soft ligand trans to itself. In all complexes studied the seleno-
cyanate ligand is Se-bonded in goid(1) complexes. "y = c.lrctronic chargo on the Au o r X ion
It should be realised that the stability constant for a complex
is not determined only by the metal-ligand bond strength. The data show very clearly that there is considerable co-
Thus, the enthalpy of substitution of chloride by bromide in valency in the metal-ligand bonds for both gold(1) and gold(II1)
[AuCl,]- in aqueous solution is -46 k J mol-', but, after con- complexes. Thus, the orbital populations indicate that the 6s
sideration of hydration effects, the estimated bond energy is and 6 p orbitals of gold are engaged in bonding, and that the
greater for the AuCl bond than for the AuBr bond [40]. charge on gold in the complexes is always less than +l.The
extent of the covalency, which is largely due to a-bonding,
increases as expected on passing from fluoride through t o
THEORETICAL STUDIES O F BONDING IN GOLD COMPLEXES iodide complexes.
For linear gold(1) complexes the simple bonding schemes
Molecular orbital calculations using the SCCC-LCAO-MO suggest that the filled 5d orbitals will play no part in bonding,
method have recently been published for some halide and and that a-bonding will use 6sp-hybrid orbitals on gold. In
pseudohalide complexes of gold(1) and gold(III), and the agreement, the calculations show that 6s and 6p orbitals on
results are of considerable interest [41, 421. gold are strongly involved in bonding in [AuX,]-, but also
For the halide complexes [AuX4]- the calculated 5d-orbital that the 5d-orbitals contribute significantly t o the gold-halide
energies for gold fall in the order d, 2 < d,,, d,, < d,, < (J-bonds. This is in accord with the ideas of Orgel on d s
-,
d,z 2 in agreement with the predictions of simple crystal field mixing in linear gold(1) complexes, discussed earlier.
theory and with similar calculations on square-planar platinum(I1)i For square-planar gold(II1) complexes Valence Bond theory
and palladium(I1) complexes. For the corresponding gold(1) predicts that gold(II1) will have the 5d"onfiguration and that
halides [AuX,] - the 5d-orbital energies for gold follow thc a-bonds will be formed using the four 5d,z .26s6pX6p,, hybrid
-,
sequence d,, , d, 2 2 < d,, , d,, < dZ2 again as expected from orbitals. Again, the calculations support this, so that the 6 p
crystal field theory. The electron configurations of A U ~ ' and orbital population is considerably greater in the gold(II1) than
Au+ are of course 5d86s06p0 and 5d'06s06p0, respectively, but in the gold(1) complexes, while the reverse is true for the 5d
the calculated orbital populations and charges on gold and orbital populations. Similar trends were observed in the thio-
halogens in various complexes are given in Table 1.4. cyanate and cyanide complexes.
THE Z'KANS-EFFECT AND TKANS-INFLUENCE t h e a-donor ability of t h e ligand. Thus, in linear gold(1) com-
plexes, for example, the gold atom is sp-hybridised so t h a t a
These two concepts are widely used In interpreting the bromide ligand in [AuBr,]- will overlap with a gold orbital
chemical properties of squaw plar~arplatinum(I1) complexes, having 50% S-character. Now, a strong a-donor ligand like
but have not been exploited similarly for iso-electronic gold(l11) AsPh, will have a particularly high demand for t h e s-orbital of
complexes. As we shall see below, however, the cunc.epts are gold in order t o give the strongest possible covalent bond. Thus,
potentially very useful and, as more structural and mechan~st~c. t h e gold orbital involved in bonding t o AsPh, in [AuBr(AsPh3)]
data are accumulated, zrr llktly t o br used morc frequently In
ratio.lalismg t h cht~m~r-a1
~ properties of both gold(1) and gold[ I l l )
T A B L E 1.5
iwmplexes.
I'he tsutzs-cfft~tis cldined ,L. tht. dbi,lty o f a hgand to Gold - -chlor~nc,a n d golti---brominv bond Icsngths in s o m e complexes
lab~lisethe llgand Irurrh to , t ~ . : f .m d h c . ~ ~ ito
c c l ~ r c ~~l'c~o i n l n g
!~gandst o this posl, icln For t~x,rrnplc.111 the cornple?i [,ZuC'I , Complex lri1ri5 11g,1nd
(PPh,)] tht. trutls c ~ f f t of~ t Ph ,P 1s q(1atr.r t hsn that o f Cl , so ( ; o l d ( I l l ) c~ornpl(~\c\
that we expect the c.hloridth [ran\ to Irii>hc~r~j.l~,hosph~nc. to h [Ph4i\sj I i\uCl4I ('I
more labile than the otntv two chiorltlr ligands tlmct., thls [AuC'l {(PPh \ ) l ('I
c h l o r ~ d eis c)xpectc~Ito he displacwl prcfcrcmtially and the I'Ptl (

incomlng hgand will bc dirertctl to the stcreochem~calposition c [ A u C : I ( C ~ F ~ ) ~ ( P(1PI ~ I ('85


c I\ [AuC12(Ph)(SPr2)I SPr,
trans t o trl~,htnylphosphinc.'I'hc. trans-cffcc-t 1s thus a klnc>t~c
PI1
concept, and we shall return t o discwss ~t m o w fully In r h a p t t ~ r
9.
'The trans-influence is defmed a5 the ability of a ligand t o
weaken the hond between the meltal and thc ligand tram to
Itself, In the ground state of the rnolrcwle. 'Thus, in contrast
t o t h e truns-effect, it is a thermodynam~c* cwncept. The trarls-
influence of a llgand is dclducwd by measuring such parameters
ds t h e metal Iigand hond lengths by X-ray diffraction or t h r
metal-ligand stretching force constants by analysls of the
vibrational spectra (;old--chlorine and gold--bromine bond
lengths for some selected complexes of gold(1) and gold(II1) will have more than 50% S-character, leaving the d o n o r orbital
are presented in 'Table 1.5. of t h e trans-ligand, Br , t o overlap with an orbital having more
From t h e gold-chlorine bond lengths for the square planar than 50% p-character. Since t h e p-orbitals are more diffuse
gold(II1) c o m p l e x e ~it, is poss~blet o deduce t h r trans-influence than the S-orbital and, hence, overlap is less effective, t h e
-
serles: Ph C,F, > PPh, > SPr, -C1 . Prom the gold-brom~ne resultant Au-Br bond is weaker and more ionic in [AuBr(AsPh,)]
bond lengths for the lmear gold(1) complexes, it follows that than in [AuBr,]-. The spectroscopic properties of gold(1) and
the trans-influence of AsPh, > Br-. gold(II1) complexes can often be rationalised using t h e trans-
I t is thought t h a t the trans-influence of a llgand is largely influence concept and we shall return t o t h e topic in Chapter
d e t e r m i n d by t h e electronegativlty of the donor atom o r by 10.
35 A. D. t i o o l s b v a n d D. 1'. Sawyer. Anul. C11c.m.. 4 0 ( 1 9 6 8 ) 1 9 7 8 .
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( 1 9 7 3 ) 2405.
.
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2 W. S. F v f c dtid K. W. I i r n l r v . Illr~c,r S C I . I.rr L... 5 (11373) 2 9 5 . R8 .I. L. B u r m r ~ s t t ~ a nr d N . J. D e S t e f a n o . Inorg. Chem.. 10 ( 1 9 7 1 ) 9 9 8 .
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3 P:. D. K < ~ r o b u s h k t n d 4. , S. C ' h t , r ~ ~ b d<kI I I ~(; XIIII,.~,\,l l ~ l : r - o l ~ l.'{ ~ ~ ~ l ~ ~ ~ ~ ~ ~ ~ , 4 0 B. I. P e s h c h r v ~ l s k ~ dn i d V. I. Belcvantsev. % h Nfwrg. Khim.. 1 4 ( 1 9 6 9 ) 2 3 9 3 .
( 1 9 7 4 ) 4:): E. D K o r o b u s h k ~ n d , G . X I I I I C ~~~r n~ d\G . P l'rddvd. I ~ I I : ~ ~ I I I ~ ~ ~ ~ ~ ) ~ ~ ~ '. ~R e~~ .n h o l d ,H. % w , i n / ~ g t r .E. 1iovt.r a n d C. Zwanziger, %. i:hrm.. 1 4 ( 1 9 7 4 )
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~, l ' t ~ t > l ~ s t ~I ,t o~nr i~i t~>, ~ 1~9. 7 - L 4 2 II. Z w a n l ~ g r r .l. . t t c ~ n h o l da n d b:. I I o v r r . %. t ' h r ~ m . . 1 4 ( 1 9 7 4 ) 4 8 9 : 1 5 ( 1 9 7 4 )
5 ,J P. R ~ l r \ III . .l. P K11k.y dnd <; S h i t ' r < ) ~(l*;d,.). \ ( ' I z ~ ~ I I I IO~ ~ ~ ~~I ~~ I Z I ~ ~ Vol ~ U ~:{,~ I ! I / I \ . 69.
4rarlcn11c Press. I . ~ , n ( l ~ r n2.n d t,d 19 7 b. ('h 10.. 4'3 P. G. .Jonrs, .J. . l . C;ur .incl C;. M. S h r l d r ~ r k .Acta Crvslollour., Scct. B . , 3 1
6 A . I. K v a b t n ~ n ,A S. K i ~ i n d n < , \S. t i h , ~ t a n r o v,tnd K t i h , i m ~ d o ~ . x( :. c ~ ~ ~ k / l l l r l r ~ ~ . ( 1 9 7 5 ) 2687.
(1974) 1 5 8 9 4 G. Bandoll. I). 4 . C'lvtncmtr. i;. M ; ~ r d n g o n ia n d L. Cattalini, J t'hrzm. S r ~ c . ,
7 B. I. Pt,shchev~tskii,(; N . Ano5hrn r n d A h1 I.:rt,nl)urc. 1 1 ~ ~ 1 \~k1u ( l t \ c l t ~ l ~ I ) u l t ( ~ tl'rurt.,.
~ (I!j7.3) 881;.
,S,SSR, l ( j 2 (l:lt;:>) 0 1 5 K:?> r j 1 i . , , , , 4 11 ,,,,, O 1 : t ~ ~ l ~( l~' i,7l l~l l l i l l ' / : , ,!I \ h \ f , 4 5 R . W . Baker ;rnd P. .I. I'.iul~ng, .J ( ' h ~ n t .S o c . , ( ' h ~ r n .Cornmurr ( 1 9 6 9 ) 7 4 5 .
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8 M. I. H r ~ t t a n Arn , S ~ . .I ti2 (197.1) 402 17 N. C'. f L w n / ~ x c r W. ~ K. Fknrit~tL< ~ n 1) d hl. .S<!t><broff% : l c , l u ( ' r v . s ~ d l ~ .%,cl
~ ~ r , B.,
9 R. J. :\damson ( E d . ) , ( ; < ) I d 11, I o l I ~ ~ r yI ,v) \c>t!llt \ ! , ~ , Y TL.h ~ i t n b c ~, >t l %lint'- R32 (197ti) 9 6 2 .
S < > u t h, \ f r ~ c ~. rI ,s ~ t i a i ~ ~ ~ ~1~9\7\ 3~ u r g l 8 .l. .l G u v . P. G. .lonc,s, M . ,l. M'IN 'ind C;. M. S h t ~ l , l r ~ c.J. k , I'h,,rrt .S<i<,, I l t ~ l l o n
l 0 .l K o r d ~ s .K A i ; ~ n ~ t , r ~a cn h d K , , l , Svvst-, .l I'/i',m 1'111,s . lil ( l : ) 7 4 ) '>l 14. I'rans.. ( 1 9 7 7 ) 8 .
,J. I h ) r ~ ~ ) h uTIr,,
e , .Stt-u(~lu~-v.s 01 111~~ 1, ivrirt,r2/s~ LVII<.\, N t ~ w Y
, < ) r k , l 9 7 l .l9 (;. .l. h r d ~ .KC(. 'l'?-01, ('llun I'<lvs /$,IS.X I ( 1 9 6 2 ) 3 0 7 .
I 1 ( a ) M. N . I / r y t ~ d n ~i;\ , h K h I ~ ~ 1 ~ 1 1 1 an(l k o ~ ,V. t 2. Krtlll~l\i.L11 , V ~ . o t . l i 1\111'f1 . 5 0 M. ( i . B. Drew ,in(J M. .l. I{Ic.<II, .J i'Ir,,m .Sot . l)ul1<111'l'rurrs., ( 1 9 7 3 ) 5 2 .
1 8 ( 1 9 7 3 ) R1 8 : f'lt~,rr~ .Ihalr.., 7 9 11:47:0 102!l!3 51 l'. 'S. B v u r s k t ~ n ~ 11., .l. ,A ~ % I ~ I ~ I L I .l. w . A ( ' r , % s,>nd .l. .l. Stc,gg<,r(l,~, III<,?-B( ' I ~ ~ ~ r r i . .
( b ) D. blclntosti ' ~ I I C I (>. A 0 / i 1 1 . l,,orc ~ ' I I , ~ l~ 5I .( I, 9 7 l i ) ZXfi!). It; ( 1 9 7 7 ) : > l . 7 ( 1 9 6 8 ) R05
H. H u b e r , l> M ~ ~ l n t o s~t i n C;d. S\. I > / I I I . I T I < , I (C .
' I I < , I I I l t; ( l ! l 7 7 ) 9 7 5 . 5 2 1%'.W. k'111stc.111. I I I I I I(. l l + , b t ~ \ o. . \ ( , / Ui ' ~ ~ \ ~ l u l l o. .S'-<
y r 1 l!.. H:Jl ( 1 9 7 5 ) fi24.
1 2 N . C. R d c n t ~ g e r .K. M. D ~ t t r l n < , r.tlld r .l. I< L>ovI(~.1,zor.C' i'111.n.. 1 3 (197.1) 8 0 5
l 3 P . L. bellon. h1 h l d ~ ~ d s w rdnd u 11. S ~ I I S < I I/I<I I. ( ,S<,#, :<!) (l!jli!J) l 7 3
1 4 J. C. M. 'T. F:~]ndhovf>ndnd C;. C. Vt.rschw,r-, .'.lcilcr. K(,.>. llu11., !) ( 1 9 7 1 ) I t i t 2
1 5 F'. Klanhcrg. E I,. Mut.ttt.rl~i~s and I.. .l i;uggenhcrg(.r, I r l o r ~ .('hcam 7 ( I 9 f i 8 ) .
2272.
1 6 H. S r h i n ~ d b d u ~ I ~r n dK. F r ; t n k ~ .i'11r)nl. 1{<,1,. 1 0 5 ( 1 9 7 2 ) 2!)85
1 7 R . I,. R i c h and H. 'Saubr. J . f'lr v,, C'hc~rn..5 8 ( 1 9 5 4 ) ti.
1 8 H. S ( ~ h r r t r d b ~ i u c. Ir. . K . h l , ~ n d l ,A . Fr'ink d n d (;. I l u t t n t ~ r t. ' h < . r r ~l3t.r.. 1 0 9 ( 1 3 7 6 )
466.
I 9 J. G . XI. \ , m Ken,. M. P A . VlW?r\ .tnd E : (Jr. Bt,t,r. ('1ii.111 1'11~s1,elI 2 8 .
(1974) 104.
2 0 4 . A . B r ? / u h c t i k o .ind H. I. Pt.cht.hevitskir. C J ~ < , ~/ r\ h~ r l r . . 56 ( 1 9 6 2 ) 20.1!4li.
.
2 1 W . 'L'. R o b ~ n s o nd n d E . S m n . J ('111~rrtS < , ( ., I)ullr,t~ I ' r o r ~ s ( 1 9 7 5 ) 7 2 6 .
2 2 V. F. D u c k w o r t h .rnd N . ('. S l e y h ~ ~ ~ j s Jttr,lg on, ( ' l ~ < ~ Xn ~(l!)fi9)., I lifil.
2 3 I. N. Bakulina a n d N . l. l o n o v . I l o l ~ lAl:(ld &ru1112 .S,sSll. l 5 5 (191; 1) 309.
2 4 E. Y . Z a n d b c r z . !\. (i t i d ~ n ~ ~ ,rnd n r v V . I P;11wb. %h 7',~1?11FL;.. 4.4 ( I 9 7 L ) til 7
2 5 R. D. H a n c o c k ,tnd N . P. F ~ n k c l s t r ~ Irzorg n. ,\'tlc.l ('1r"m 1.1,11.. 7 ( l l l 7 l ) -477.
2 6 R . S. N v h o l n ~ P , r o c ('h<,n~ S ~ J C ( I Y(i l ) 2 7 X
2 7 L. E. Orgel. J. C'hcm. Sot..( 1 9 5 8 ) 4 1 8 6 .
2 8 C. K . .Jdrgensrn a n d J. P o u r a d ~ e r J. ('hint. I'hys., 6 7 ( 1 9 7 0 ) 1 2 4
2 9 C. J . Hawkins. 0. M o e n s t e d a n d .I. Hjrrrum. A c l a C h c m S c u n d . . 2 4 ( 1 9 7 0 )
1 0 5 9 ; L. H. S k i b s t r d dnd J. B j e r r u n ~ A . e t a Chc,rn. S c u n d . Srpr A . 31 ( 1 9 7 7 )
155.
3 0 L. M. G e d a n s k v a n d L. G. Hepler. k'nyc'lhurd I n d T i ~ hIJull., 1 0 ( 1 9 6 9 ) 5.
31 N. P. F i n k e l s t r i n a n d H. D. H a n c o c k , (;old Hull.. 7 ( 1 9 7 1 ) 7 2 .
3 2 A. H a k a n s s o n a n d I,. J o h a n s s o n , C h e m Scr.. 7 ( 1 9 7 5 ) 2 0 1 .
33 V. P. Kazakov. A . I. Lapshin.and B. 1. P e s h c h e v ~ t s k i i ,%R. .Vr,r>r.p K h ~ m . ,9
(1964) 1299.
3 4 L. H. S k i b s t e d a n d J. Bjerrum, A r t a C h e m . S c n n d . . Scv A.. 2 8 ( 1 9 7 4 ) 7 6 4 .
CHAPTER 2 HALIDES O F GOLD

The known halides of gold, together with some thermo-


BINARY COMPOUNDS OF GOLD dynamic data 131, are listed in Table 2.1. It can be seen t h a t
only fluorine gives a gold(V) derivative, while iodine gives only

TABLE 2 1

Hn1ldt.s <,F gold and thr~rmodynammcdata a t 298 K for c r y s t a l l ~ n e


compobnds

Ljgk/, Allf*'/ AGJ


('ornr~c)und ('olour g cm kJmol l k.1 m01 '

The monomeric compounds AuFl and AuI) certamly exist in


the gas phase when gold is heated t o about l ZOO 'C: In an 'I'herc. 1s 110 cv~drnc.rfor thc c>x~stt.nc~ of AuF and c.st~matrd
atmosphere of hydrogen or dt.uterium, respectively. Deta~led thermodynamic. data ('Tablr 2 1)suggest that ~tw ~ l bt. l unstable
spectroscopic studies have been carried out on these compounds, w ~ t hrespect t o dlsproport~onatlont o gold and AuF3.
and as a result the bond d ~ s s o c i a t ~ oenergy
n a11d Au- H bond AuF, was f ~ r s prepared
t 141 by h e a t ~ n gAuF,.BrF,, formed
d ~ s t a n c eare calculated t o be 310 k J mol-' and 152.5 pm, by dissolut~onof gold In BrF,, a t 300 'C. The product formed
respectively [ 2 ] . m this way is contaminated with bromine, and the pure com-
pound is best prepared by reactlon of either gold(II1) chloride b u t is associated by the presence of fluorine bridges. The
or gold powder with fluorine at high temperature 15, 61. structure is n o t known with certainty but, from powder X-ray
Gold(II1) fluorlde can be sublimed a t 300 "C' under vacuum
photographs, a structure similar t o that of RuF, is suggested.
t o g v e bright golden-yellow needles. It decomposes a t 500 " C
This is tetrameric with bent R u F R u bridges, each ruthenium
t o gold and fluorme, and IS a powt.rful fluormating agent,
having approximately octahedral stereochemistry. AuF, is a
causlng b r n m w to burn I t forms the ,iddu<ts I u F , RrF,,
dark red solid which melts over the range 75-78 "C, and can
I u F , %.F, and N O [ ,ZuF, ]
be sublimed under vacuum. It combines with oxygen and
AuF, is diamagnetic s h o w n g that gold( l11 1 has t h e usual fluorine t o reform [ 0 2] [AuF61, with XeF2 t o give
low s p ~ ndn cwnflgurat~c~n, and thc ( ompound has a unlyue
[ X e 2 F 3 ][AuF,] and with NOF t o give [NO] [AuF,].
structure whic h I , illustr;h~d F i g :l 1 i t (.,in hr drscrlhtd Attempts have been made t o prepare gold(V1) fluoride,
e r ~ d tgl rh t , h ~di i i , i i i t k ) c , i \ n i t I , tht* hai:~,btbing
da a f l ~ ~ o r i til~
which is expected t o be the most powerful oxidising agent of
rosc 11rlkmi \\lth M'~>;II\I>T f l i : r ~ r i l ~hridgt,.
f~ F;ic h gold dtom the third transition serics mt.tal hexafluorides, h u t all attempts
fr)rms strong bond5 to t ~ b otcrnl~n11 <incltw,vr, is bridging (
have failed.

( b ) Chlorides of gold

Reactwn of chlorine with gold may p v e cither gold(1)


chloride or gold(l1I) c h l o r ~ d edeprwd~ngon the rtactlon con-
ditions. A claim that Au('1, could hc formed has been disproved.
IJI
The thermodynamics of the gold chlorin(. s y s k m have
Flg. 2.1. The structure of A u F , . ( a ) Part of a helical chain, ( h ) t h e CO
been thoroughly studied ( 3 , 9, 101, and some of the more
ordmation a b o u t gold(I11).
important conclusions arc discussed here. At room tempera-
fluorides t o g v e overall a square-planar arrangement of ture gold(1) chloride is metastable, and very slowly dispropor-
fluorine atoms ahout t w h gold centre These square-planar tionatcs t o gold and gold(ll1) chlor~de,Au2C1, At a chlorine
gold units are linked togethtlr by thr. bridgmg fluorines t o g v e pressure of one atmosphere, Au2C16 exists as t h e only species
the helical-chain structure 'I'herc 1s then add~tionalweak cross- in both solid ( S ) and gaseous ( g ) phases a t temperatures below
linking in w h ~ c hthe terminal fluorines occupy positions above 254 OC. At temperatures hctwecn 254 "C and 282 "C, AuCl(s)
and below the square-planar gold(lI1) centre of another chain, rxlsts together with Au,Cl,(g), while above 282 "C Au(s),
t o g v e an approximately tetragonally d ~ s t o r t c doctahrdral Au2Cl,(g) and Au2Cl,(g) coexlst. Thus Au2C1, can b e pre-
environment about each gold atom. pared by reaction of gold with chlorine a t temperatures below
Gold(V) fluoride [7, 81 can be prepared by thermal de- 254 " C . Typically a rapid flow of c h l o r ~ n egas is passed over
composition of either [ K ~ F ] + [ A u F ~o ]r of [ 0 2J S [ A u F 6 ] . gold a t 240 'C, when Au2C1, is formed and sublimes t o g v e
red crystals on the cooler parts of the tube. Alternatively, the
reaction can be carried o u t a t 250 " C in a salt bath [l11.
Large crystals of the yellowish-white AuCl can be prepared by
vapour transport of Au,Cl,(g) in an atmosphere of chlorine.
Gold(V) fluoride is diamagnetic so that gold(V) has t h e low Thus Au,Cl,(s) contamed a t one end of a tube is heated t o
spin 5d6 electron configuration. It is certainly n o t a monomer,
247 'C, and is deposited as AuCl(s) a t the other end which is
Fig. 2.3. The s t r u c t u r e of Au2C16

Fig. 2.2. The s t r u c t u r e of AuCl

and gold(II1) sprcies including [AuCI,(OII, ) ] is very rapid in


water, and AuC1 must he stored in a desiccator t o minimise 'fhesr reactions do not take place, however, if the aromatic
this mode of decomposition. In the gas phase goldil) chloride compound contains a suhstitucnt which can co-ordinate t o
exists as the dimer Au,CI2, which may have a vyclic structure, gold. Thus bc?nzonitrile and a z o b ~ n z e n tform
~ simple nitrogen-.
and for which the enthalpy of dissociation t o monomt>ric donor complexrs of the type [ IAuC:l, ] 1191.
AuCl is 68 k J mol '
[l31 . A particularly stable graphite insertion compound of
The most typical reaction of AuC1 is t o form complexes of conlposition C , AuCI, is formed by direct reaction of
the type LAuCl, for which the ligand L may he ammonia, graphite with [iZu,Cl,]. The stability is due t o the short inter-
pyridine, a trialkylphosphine, a dialkylsulphide, carbon mon- planar distance of 680 pm, n o d o u b t made possible by t h e
oxide, an alkene and many others. These, and complexes planar structure of [Au,CI,]. This dimeric structure of
derived by addition of more than one equivalent of t h e ligand [Au, Cl,] persists in the gas phase [g, 141, and the enthalpy
L, will b e discussed in Chapter 3. AuCl dissolves in concentrated of dissociation t o monomeric [AuCl,] is estimated t o b e
sodium chloride solution t o give Na[AuCl, ] but the [ AuC1, ] 77 kJ mol-' .
ion is itself decomposed by water t o give Au and [AuCl,] . Many claims for the formation of t h e compound "AuC12"
Gold(II1) chloride has t h e dimeric chlorine bridged structure have been proved t o be false, b u t a black compound of this
shown in Fig. 2.3, in which each gold atom has square-planar empirical formula is formed by reaction of gold(II1) chloride
stereochemistry . in thionyl chloride v i t h a deficiency of carbon monoxide.
The reaction gives [Au(CO)Cl] in the first stage and this iodide ions. However, many gold(II1) complexes readily
reacts with excess of [Au2C1,1 as follows: oxidise iodide t o iodine, and it now seems likely t h a t t h e
isolated compounds with empirical formula Au13 are actually
[Au(CO)Cl] + (Au,Cl,) 4 + Au, (CO)Cl,
compounds of gold(1) with 1, rather than gold(ll1) iodide
[ 2 0 ] . The compound AuI, readily eliminates iodine t o give
gold(1) iodide, which may be obtained directly by reaction
The product XuClz is diamagnetic and so is most 11kely a
of iodide with aqueous solutions of Ii[AuC14] or, slowly, by
mixed gold(1) gold(II1) species; this is confirmed by the
direct reaction of gold with iodine a t elevated temperature.
structure determination [ 1 9 b ] which shows the p r t w n c c of
It forms yellow crystals which are much more stable t o water
cyclic [ilu4C18] nlolecules with linear gold/I) and sy uare
than AuC1, probably due t o its much lower solubility [ 2 1 ] .
planar gold(II1) centres as shown in Fig 2 3
It dissolves in water in the presence of iodide ions t o give
[ A u I , ] , and in i o d i d e iotlinc solutions t o give mixtures of
[ A u I z ] , a n d [Aul, 1 .
The structurt. of AuI is likv that of AuC1. Each gold is
lint.arly co-ordinatid t,o two iodine atoms a t a distance of
262 pm with four more iodinrs further away at 3 0 8 pm [ 2 2 ] .

Fig. 2 . 4 Thc s t r u c t u r e ot r\u4Clh

( c ) Bronzidcs and iodides of' gold Gold(1) cyanide is r ~ a d i l yformed by heating K[Au(CN), 1
with hydrochloric acid. It forms yellow crystals, which have
Gold(lI1) bromidc is formed hy thc exothermic reaction of a polymeric structure with linear A u C N A u C N chains. It is
-

gold powder with liquid bromine. It forms dark red-brown insoluble in w a k r b u t dissolves readily in the presence of
crystals. The structure is dimeric like that of [Au,Cl,] though cyanide as the romplcx ion ( A u ( C N ) , ] . This reaction has
the full crystal structure has n o t been completed (131. Its bcen invoked as the final step in t h dissolution
~ of gold by
chemic.al properties also resemble thosc of [Au,Cl, 1. Thus ~t cyanide in the prcwncc o f oxygen (231 .
reacts with nitrogen donor llgands, L, t o g v e complexes Anhydrous gold(lI1) cyanide is n o t known, probably due
[LAuBr, 1 and IS reduced by tertiary phosph1nc.s and arsincs t o its inability t o dimt>risclike thc gold(l11) halides, b u t the
and by dlalkylsulphides to g v e conlplexes [LAuBr] . On heat- complex A U ( C N ) .~3EI,O can be prepared b y dehydration of
Ing t o a b o u t 2 0 0 "C, [Au,Br,] decompostls t o bromine and solutions of kI[Au(CN), 1 . Its structure is n o t known, b u t i t
AuBr. Again like the corresponding chloride, this is moisture decomposes readily t o gold(1) cyanide on being heated.
sensitive, decomposmg t o gold and gold(II1) species, and forms An alternative route t o gold(1) cyanide is b y heating
complexes [LAuBr] with many ligands L and the complex Ion dialkylgold(Il1) cyanides, and this method has also been used
[AuBr,] with bromide. AuBr decomposes t o t h e elements o n t o prepare gold(1) thiocyanate [ 2 4 1. Thus, heating
bemg heated above 250 "C. [(Et, AuSCN), 1 in xylene a t 1 2 5 "C gives AuSCN as an
Several claims have been made t h a t gold(II1) iodide can be insoluble colourless powder, which decomposes t o gold a t
prepared from solutions of gold(II1) complexes containing 1 4 0 "C. AuSCN dissolves in water or alcohol in the presence
of thiocyanate Ions t o give [Au(SCNJ21 , which d e ~ o n ~ p o s ~ s in cyanide or polysulphide s o l u t ~ o n sThe. standard Gibbs free
rather rapidly in water. The potassium salt K [ A u ( S C N ) ?1 can energy of formation A G f - 1s +29 kJ mol-I . In t h e gas phase
be obtained from ethanol, however. a t high temperature Au,S molecules apparently exist [31].
Gold(1II) sulphlde can be prepared b y reaction of H,S wlth
OXIDES A N D HYDROXIDES O F GOLD [Au,Cl,] In anhydrous ether a t low temperature. Attempts
Gold(l1I) h y d r o x ~ d eAu(OH), 1s fornlrd hy a d d i t ~ o no f t o prepare ~ttn aqueous solution lead t o reduction t o metallic
sodium hyrirolilde t o solutions contamliig [AuC'l, j 'I'his gold. The black powder decomposes t o t h e elements on being
hydroxtde c m be dehydrated to gtvt3 flrst . Z u ( 0 ) 0 Hand then heated t o 200 "C. lt dissolves with decomposition t o
A u 2 0 3 .r!u2O3 decomposes t o gold a i d oxygen above 1 6 0 "C' [lZu(('N)2 1 in cyanide solution.
The most recent dt.terrnlnatlon g~\c.s 1H,"( . 2 u , O , ) = 1 3 O + Two selenides of gold are known, AuSe and Au,Se3. There
2 3 k J mcrl ' , and , \ U 1 u z0,acts 3s a truc rnc~almt>tal o x d r x e two crystallme forms of AuSe, both of whlch form mono-
i
r

riec r r c d t ~byhtt~rnM ~ t h7 1 .X 125. 26 I c lmic crystal?. The 0 form of AuSe contains gold in t w o forms,
(;old( l [ lI i ~ b d r ~ \ l d~ <t ~' c LSi ~ \ \ ~ t hiIc3r( I I I U ~ I <<I< fjf.111~ onc w ~ t hh n t w co-ordinat~ont o t w o selenium atoms and t h e
heated in 3 wild t u k ,it 150 - ( ' for 2 wt.t.k< to givc3rml other with square-planar co-ordlnatlon t o four selenium
transparmt crystals of ZuO('1 'I'hf. gold( l l l ) o x ~ c l rc~h l c w d ~ ~ atoms It 15, therefore, hest represented as Au(I)Au(III)Se,.
decompows to the elcments at 290 "C' 1271. ~ L I ( O ~isI ) , Gold rcac ts directly wlth tt~llunumt o glve AuTe,, whlch
gcncraily known as aurtc acxt s1nc.t. 11 I)c,havc.sas a n c ~ ' i I \ .IL i t i also occurs In the rn~nc~rals calaverltr. and sylvanlk. The
Thus ~t dlssolves rmdily in K011 solution to g i v ~aftrhr t w p o r - crystals c o n t a n linear TrAuTe units. The standard enthalpy
ation K , I u O , t'3fi20 w h ~ probat)ly h ~ w n t a i n sthc [ , \ u ( O l l ) , j of formatlon 41ir" 1s ( 1 8 . 6 4 3 ) k J mol ' 1331. In addition
Ion. Neutraiisatlon of buc.h w l u t ~ o n ,leads to rr3prcc~ p i l a t l o n .Zu,Tc, occurs in tht* rnlnr.ra1 m o n t b r a y ~ t cand a c-,npound
of gold(lI1) h y d r o x ~ d c Although the hydroxide is solublc t o ,,
of composition Au'l'e, is formed by reduction of solutions
some extent in s u l p h u r ~ cor n l t r ~ cacld, t h c 1s ~ no midence contrunlng gold(II1) and tellur~um(IV)with hydrazine [ 3 4 1.
for formatton of the ayuogold(ll1) ion In the s o l u t ~ o n s'I'herv In addition t o thr, blriary selenldcs and tellurldes, the mixed
1s e v ~ d e n c ethat the spccles [f12.CuO, ] , [ I I A L ~, O l 2 and compounds AuBrSe, LZUI'I'~, AuClTe,, AuRrTc, and AulTe,
[ AuO 1 uc formed on treating ,Zu(OH), with ~ncrrasingly are known Typcally, A u l T t ~ ,1s prcymrd by reaction of
concentrated hytiroxlde solutions, h u t thc structures of thcsc elemental gold and tellurium with h y d r i o d ~ cacid In a sealed
~ o n are
s n o t known 1281. tubr a t a temperature of 450 "C, the mixture then bring cooled
Reports of the cxistencar~o f gold(l) oxide and gold(1) slowly t o 1 5 0 "(' over a period of ten days [35, 361. The
hydroxide are now regarded w ~ t hsceptictsm, b u t the o x ~ d a t i o n compounds AuXrre2 all exhibit metalhc. conductivity, and t h e
of CsAu with oxygen at 400 "C has been shown t o gIve the structures have gold co-orclmated t o four tellurium atoms 137 1.
aurate(1) derivative CsAuO 129 1 . The structure of AuRrSe contains gold in syuare-planar co-
o r d ~ n a t l o nwlth some gold atoms co-ord~natedt o f o u r selenium
SUI.PHIDES, SELENIDES AND TELLIJRIDES O F GOLD atoms and some t o two brom~nr.and t w o selenium atoms [38].

Gold does n o t react directly wlth sulphur, b u t the com-


GOLD(II1) FLIJOKOSULPHATE AND NITRATE
pounds Au,S and Au, S, can be prepared. ( h l d ( 1 ) sulphide IS
formed b y reaction of [Au(CN), 1- with 1-1,s.It is a black- Reaction of gold with bromine(1) fluorosulphate a t 65 "C
brown powder which is only very slightly soluble 111 water (301 gives a complex A u ( S 0 3 F ) , . 213rS03 F which loses BrS0,F on
(K,,, = [ A ~ f l[*s 2 '1 4 X 10-''%t 25 " V ) but which ~ I S S O ~ V E S being heated under vacuum t o give Au(SO,F),. This is a bright
orange-yellow solid which melts at 94 "C. Its structure is n o t 4 A. G . S h a p e . J C h r m . Soc.. ( 1 9 4 9 ) 2901.
5 L. R. Asprev. F. H. Kruse. K . H. J a c k a n d R . Maltland. lnory. Chem.. 3 ( 1 9 6 4 )
known but lt appears to be polymeric wlth brldging fluoro- 602.
sulphate groups [39] 6 F. W. B. E ~ n s l e i n P. . K. Rao. J . Trotter a n d N . Bartlett, J . Chem. Soc. A , ( 1 9 6 7 )
478.
Dissolut~onof A u 2 0 3 I n concentrated n i t r ~ cacid does not 7 J. H. Hollowav a n d G . .I. Schrr>bilgen.J . C'hrm. Soc. Chem. C o m m u n . , ( 1 9 7 5 )
g v e anhydrous gold(II1) nltrate but t h e complex acid 6 2 3 : V. B. Sokolov. V. N . Prusakov. A . V . R y ~ h k n v a n dYu. V. Drobyshevskii,
Uokl. Ahad ,Vaul; SSSH. 2 2 9 ( 1 9 7 6 ) 8 8 4 .
H [ A u ( N 0 3 J 4 ]. 3 H 2 0 . It has been cla~medthat r e a c t i o n of X M. J . Vasile, T . J . R ~ c h a r d s o n ,F. A. S t c n e a n d W. E. Falconer. J. Chem. Soc.,
this product with N 2 0 , followed h y heating of the product Llaltori I'rans. ( 1 9 7 6 ) 3 5 1 .
9 E. M. W . Janssen. F. Pohlmann and G. A. Wiegcrs. J Lc'ss C o m m o n Met..
under vacuum gves a golden-yellow suhhmate of Au(NO,), 4 5 (1976) 261.
at 80 "Cl4 x 10 ' Torr. The yield was very low and the 10 E M . W . .lansscn. J . C . W. Folmer a n d G . A. W~egers,J. Less-Common Mrt.,
3 8 (1974) 71
characterisation r e l i e d e n t ~ r e l yon analysis for gold [40J. The 1 1 T. Mundorf a n d K . Uchnrcke, % Naturforsch.. 'l'ril R . 2 8 ( 1 9 7 3 ) 506.
claim must therefore be considered doubtful though cwmplex 1 2 I). B. I)cll'Xn~ict!a n d F. Caldera//c,. C m : Chim. Ital.. 1 0 3 ( 1 9 7 3 ) 1 0 9 9 .
1 3 .l. Strarhlc a n d K . P. I,ot3rcher. % Nalurforsch.. 'l'eil B, 29 ( 1 9 7 4 ) 266.
nitratoaurates(III), LI'[Xu(NO , l 4 l , arc>w e l l c.haractrr~scd I 4 M . h . % v r i . l n ~ ) abn d G . A . Khlebnikova. Izr'. L'~ss11.I:chcbrl. Laucd.,
[411. T s ~ w t n Mcfal . l 6 ( 1 9 7 3 ) 1 1 2 .
1 5 C . Tdgildvlnl, LI. Bt,lluco a n d G. Pilloni, Hic. Sct. Part,, 2. Scz. A, 3 ( I 9 6 3 )
889.
16 K. Huttel, M. Hcinherrnrr a n d U . N o w a k . ('hem Rpr., 101 ( 1 9 6 8 ) 3 7 6 1 .
NITRIDES AND OTHER (;ROllP V DERIVATIVES .
17 K . S. Ltddlc a n d C . Parkin. .l. Chcm. S o c , Chrnl. Comrn ( 1 9 7 2 ) 26.
1 8 P. W. J . d e Graaf, J . Boersnra a n d G. .I. M. van d e r Kerk. J. Organomet.
N o simple gold nitrides are k n o w n h u t there was great Chcrn . 1 0 5 ( 1 9 7 6 ) 3 9 9 .
interest in the Middle Ages in an explosive substanw called 19 ( a ) F . Caldera//o a n d D. B. Dell'Anrlco. J. O r g a n < l r n ~ tChern.,
. 1 9 7 4 . 76. C59.
(b) I). R. Dell'Anrlro, F. C a l d e r a l l o a n d F. Marchetti. J. Chem. Soc.. Dalton
fulminating gold. This is formed by reaction of Au,O, with 'l'rar~s..( 1 9 7 6 ) 1 8 2 9 ; l). H. I)rll'.Am~co, F. Caldt*ra/.lo, I.'. Marchetti, S. Merlino
aqueous ammonia or ammonium salts, by reaction of a a n d G . Prrcgo. J Chc,m S o c . C'hrrn ('ommun.. ( 1 9 7 7 ) 31.
2 0 .l. L. Rydn, Iftorg. Chc,rrt.. 8 ( 1 9 6 9 ) 2 0 5 8 .
gold(II1) salt and an ammonium salt with base and by several 21 A. Hakansson a n d L. Johanssc~n.Chern. Scr.. 7 ( 1 9 7 5 ) 2 0 1 .
other routes. It has been variously formulated as AuN . NH3 . 2 2 R . W. G . Wyckofi. Cryslal Slructurc~s,Vol. l . Interscience, New York. 2 n d ed..
1 9 6 3 , p. 1 5 9 .
13 H2 0, Au(NH)NH2 or A u 2 0 3 . 4Nf13 and probably several 2 3 1. A . Liako\,skl~a n d C;. F. Cherkasov, Chern. Ahstr.. 8 1 ( 1 9 7 4 ) 1 7 3 4 7 1 .
different mixtures of compounds may he formed depending 2 4 W . 1,. Gent and C . S. (;~hsc,n,d.Chcrn. Soc., ( 1 9 4 9 ) 1 8 3 5 .
2 5 S. .l. Ashcroft a n d E . Schwarlrnann. d . Chrnt. Soc.. Faraday 'I'rans. 1, 6 8 ( 1 9 7 2 )
on the preparative route. All cletonatcl to give gold, nitrogen, 1360.
ammonia and water. 26 J . P. Huarc. E:lc~ctrachirrr Acla. 11 ( 1 9 6 6 ) 2 0 3 .
.
27 E. S c h w a r t n l a n n . K . S c h u l ~ rand J . Mohn, % Nalurlr~rsclt 'l'cil B, 29 ( 1 9 7 4 )
The compounds Au,P, ( A H T -~-97.5or 48.5 k J m o l - l ) -
56 I .
and AuSb, ( A t i f " - 13.1 k J mol-' ) can he prepared by 2 8 t l . L. .lohnst<,na n d El. L. [,eland. .l Ant. ('hcni. S o c . . 6 0 ( 1 9 3 8 ) 1 4 3 9 .
29 K. H e s t c r ~ n a n na n d R . Hoppe. %. Artory Allg. Chc,m.. 3 6 0 ( 1 9 6 8 ) 1 1 3 .
direct combination of t h e elements at high temperature 1421. 3 0 A . d r Cugnar-I'ailliolet a n d .l. P o u r a d ~ e r C. . R . A c d Sci.. Ser. C , 2 7 5 ( 1 9 7 2 )
551.
A u S b ? has the electrical properties of a metal [ 4 2 ] , and has
:I1 S. Smoes. F. Mandy. A. V. Auwcra-Mahicu a n d J . Drowart, Bull. Soc. Chim.
the cubic fluorite structure, the shortest A u S b and Sh-Sh Bcly.. 8 1 ( 1 9 7 2 ) 45.
3 2 J . R . Crctier and G . A. Wiegcrs. Matcr. Hcs. Rull.. 8 ( 1 9 7 3 ) 1 4 2 7 .
distances being 276 and 286 pm, respectively [ 4 3 ] . 3 3 K . F . L. A n d o n , .l. F. Martin a n d K . C. Mills. J. Chem. Soc. A , ( 1 9 7 1 ) 1 7 8 8 .
3 4 F . H. Hnwie a n d C . K. Veale. J Inorg Nucl. Chcm.. 28 ( 1 9 6 6 ) 1 1 4 9 .
3 5 A. Kabcnau a n d H . Kau. Inory. Synlh.. 1 4 ( 1 9 7 3 ) 1 6 0 .
3 6 A . Kabrnau. H. Kau and G. Kosenstein. A n g c u ~ .Chem. Int. 8:d. Enp.. 8 ( 1 9 6 9 )
REFERENCES 145.
37 H. M. Haendler. D. Mootz. A. Rabenau a n d G . Rosenstein. J. Solid S t a t e
l E . Wiberg a n d H. Neumaier. lnorg. Nucl. Chcrn L ~ l t . 1, ( 1 9 6 5 ) 3 5 . .
Chcm 1 0 ( 1 9 7 4 ) 1 7 5 .
2 U. Ringstrom. Nature, 1 9 8 ( 1 9 6 3 ) 9 8 1 ; A r k . Fys.. 27 ( 1 9 6 4 ) 2 2 7 ; 5. P. 3 8 D. M o o t / . A. Kabenau. H. Wundcrlich a n d G . Rosenstein. J. Solid S t a t e Chem.,
Desclaux a n d P. P y y k k o . Chem. Phys. L e t t . , 39 (19 7 6 ) 3 0 0 . 6 (1973) 583.
3 L. M. Gedansky a n d L. G . Hepler, Engelhard lnd. Tcch. Bull., 1 0 ( 1 9 6 9 ) 5 39 W. M. J o h n s o n . R. Dev a n d G . H. Cady. Inorg. Chem.. 1 1 ( 1 9 7 2 ) 2260.
CHAPTER 3
40 B. 0. Field and C . J. H a r d y , J . C h e m . Soc., ( 1 9 6 4 ) 4428.
41 C . C . Addison, G . S . R r o w n l e e and N . Logan. J . C h e m S o c , D a l t o n 'I'rans..
(1972) 1440.
4 2 W , D. Johnston. R . C . Miller and D. H. Damon. J I,t%s Common .11c2t.. 8
( 1 9 6 5 ) 272; C. E . Myers. T. J . Conti and N. F. Mar1ey.J. 1 . t . s ~ C o m m o n 2 W ~ z t , GOLD(1) COMPLEXES
48 ( 1 9 7 6 ) 213.
43 S. Furuseth. K . Selte and A . K l ~ k s h u s ,A c t a C h f m . S c a n d . 19 ( 1 9 6 5 ) 735.

In this c h a p k r the complext>sof gold([) are discussed


accord~ngt o the nature of the donor atom(s) of the ligand(s)
complexed t o gold. We shall examine complexes with group
I V , V, V1 and V11 donors in that sequence. Many of the group
TV donor complexes wlll h e discussed in subsequent chapters
on organogold complexes and on compounds with gold-metal
bonds, and hence only the carbonyl, cyanide and alkyl and
aryl isocyan~dec o m p l ~ x e sare considered here.

CARBONYL COMPLEXES [ I ]

The only well-characterised compound is [AuCl(CO)].


This was or~ginallyprepared by treatment of CO with solid
AuCl a t 9 0 'C. The carbonyl complex is a white solid which
sublimes in a stream of CO, b u t which dissociates back t o
AuCl and CO on being heated under vacuum. It can be pre-
pared more easily by bubbling CO through a suspension of
AuCl in benzene, in which solvent the product [AuCl(CO)] is
soluble, or by bubbling CO through a solution of [AuzCl,] in
tetrachloroethylene a t 1 2 0 'C. In the latter case phosgene is
formed [2].
[Au, Cl,] + 4 C 0 + 2[AuCI(CO)l + 2COC1,
A particularly convenient preparative route involves dehydra-
tion of the readily available tetrachloroauric(I1I) acid,
H[AuCl,] . 3 H 2 0 , with thionyl chloride t o give [Auz Cl6 ] ,
which is treated in situ with carbon monoxide t o give
[AuCl(CO)] and phosgene [ 3 ] . Anhydrous conditions are
necessary for the preparation since decomposition t o gold and
CO occurs very readily on reaction with water. Even moist air
or alcohol decomposes [AuCl(CO)] in this way.
CHAPTER 10 TABLE 10.1

Infrared a n d Kaman spectra of ions [ A u X 2 1


SPECTROSCOPIC STUDIES OF GOLD COMPLEXES

Most published papt>rson gold compounds now contam


spectroscopic data, most commonly from t h e infrared and
r1.rn.r. spectra. It would 1~ ~nappropriatrt o attempt t o give
a c u m ~ ) r t ~ l i c ~J ~~YsYi JvL I I o
~ ~f such sptSc.tra,and o l ~ l yvnough
(lata to show the klntl o f ~ t i f ~ ~ r r n aatbi o~ln~ strr~cturc
t and
h o n d ~ n gin g o l d ~~)m[)lc.;t)s which can hr. o b t a ~ n c dfrom
spwtroseoplc studltls w ~ l bc. l given here.

S t u d ~ e of
s g o l d l i g a n d stretching and other vibratmns by
mfrarcyi and Rarnan sprctroscopy can 3 1t.1~1uscful mformation
about the metal-ligand bond strength and t h e d e ~ ~ of e eco-
valency in the metal-ligand bond. 'I'he metal--1igand stretch-
mg frcyuency is dctermmrd by t h c masses of the metal and
ligand, by the stretching force constant whlch is related t o t h e
strength of the metal-hgand bond, and by couplmg o f this
vibrat~onwith other moltwdar vibrational modes belonging
t o thc same symmetry species. Idcally thereforcl, when com-
parmg metal ligand bond strengths t h e stretching force
constants should be calculated b u t this 1s difficult except for S t r t ~ t c h i n gforce, constants, l: / N m l, f o r s o m e linear molcru lw and ions
the most symmetrical molecules. We shall discuss such mole-
cules first.
-
(a) Linear molecules [A u X ,

There are three normal modes of vibration for these mole-


cules, namely t h e symmetric stretching vibration (v,, symmetry
C,'), the bending vibration (v,, symmetry nu)
and t h e asym-
metric stretching vibration (v,, symmetry C,'). v, is Raman
uncertainty of the assignments, but some trends become appar-
ent. Thus, there is a remarkable change by a factor of two in
the energies of the d-d bands between [AuCl,]- and [ Au14]-,
and the bands are all at lower e n e r g ~than ~ for t h e correspond-
ing [ p t x 4 j 2 -ions. This latter observation is exceptional t o
t,he general rule that increase in oxidation state leads t o higher
ligand-field splittings. It is suggested. that the u *-orbital
5d,2 ,.2 has more pure metal character for complexes of
Au3+than for p t 2 + ,but that the 5d,, level is more strongly
destabilised by interaction with the ligand n-orbitals for
A U ~ +than for R*+.The result is that the separation 5d,,. -+

5d,2 ,: is less for gold(Tf1)comploxrs than for platinum(I1)


comp1exr.s [73, 761. The very low separation in [ A L & - is
due t o w r y strong ligand-to-metal T-bonding in this complex.
Anothcr way of looking a t this is to say that the orbital 2h,,
(5d,, ) has consitlrrabie ligand character, and hcncr that t h e
transition 20,,(5d, ,,) -t 30 ,,(5d, L ,.2 ) has considerable ligand-
to-metal charge-transfer character and its energy takes on the
character of such a transition, decreasing sharply for the larger
halidc ions.
As well as the gold(II1) complexes discussed above, elec-
tronic spectra have been discussed for [Au(N,),]- [ 8 1 ] ,
[ A ~ ( N F I , ) , ] "[ 7 3 ] , [ A u ( C N ) , ] [ 7 3 ] and for several other
m i n e complexes of gold(I11) [79, 80, 821. It has also been
noted that the ligand-to-metal charge-transfer transitions in
organogold halides (R,AuIir), and [R,AuBr(NH,)] are at much
higher energies than in IAuBr,] , and the result is ascribed t o
the strong destabilisation of thc c;*-orbital 5d,z ,z on gold
by the strong U-donoralky l groups R 1831.
Although the u.v. spectrum of [Au(CN),]- is clear up t o
50,000 cm-', the spectrum of [Au(CN),]- contains many
bands below this energy. These bands are due t o metal-to-
ligand charge-transfer transitions, which are, as expected, a t
lower energy for the gold(1) than for gold(II1). A simplified
molecular orbital energy level diagram for [ Au(CN ), 1- is
shown in Fig. 10.4, and detailed analysis of the U.V.spectrum
of [Au(CN),]- confirms that the order of d-orbitals is 5dzz 2
5d,,, 5dxz- - , 2 > 5dXz,5d,,, taking the z-axis as the molecular
axls. Since t h r 5d,, and M, 2 , L arc. non-bond~ng,~t1s clear
that 5dy2 lssl~ghtlytlestah~lwtlt)y tr-l)ond~ng, and that 5d,,
and 5d, are slightly stabd~scdt)y ~ - t ) o n c l ~ tnog vacant T*-
orbitals of t h e cyanidc l~gands.tlowovcr the total splitting
of the 5d I r v t ~ is l ~(.st~matcdto t)t. no Inore than 5000 cm l,
mdicating t h a t thc ten 5d-clc~h-ons are cwcnt~allycore
electrons and arc ~nvolvedonly weakly In t~onding.'rhclre is
reasonable agreement h t w c ~ nthc o b s r r v f d and calculated
t r a n s i t ~ o nenergies, lending support t o those conclusions
[74, 841 . T h e U.V.spclctra of [ A u X , ] - , X = h a l ~ d e have
, not
hccn reported, hut are t1xpc~ctcdt o c o n t a ~ nonly very high
mcrgy bands, s~ncr.d cl transitwns are not possible for gold(I),
and Iigand-to-metal charge.-transfer trans~tionsare expected
to bt. a t high c3nergy for this low o x ~ d a t ~ ostate
n of gold.

REFERENCES

1 P. Braunstem and K . .I. H. Clark. J. Chcm. Soc , /)a11011'rrans., ( 1 9 7 3 ) 1 8 4 5 .


2 G . W . Rice and R . S . Tohias, Inorg. Chr,m., 1 4 ( 1 9 7 5 ) 2 4 0 2 : 1 5 ( 1 9 7 6 ) 4 8 9 .
3 L. H. Jones, J . Chcm. Phys., 4 3 ( 1 9 6 5 ) 5 9 4 .
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4 9 F . C o l e t t a , R . E t t o r e a n d A. G a m b a r o , Inorg. Nucl. C h r m . Lctt., 8 ( 1 9 7 2 ) 6 6 7 . CHAPTER l1
5 0 H , S c h m i d b a u r , H. F . Klein a n d A. S h i o t a n ~ ,C h e m . B e r . , 1 0 4 ( 1 9 7 1 ) 2 8 3 1 .
5 1 G . E. Glass, W . B. S c h w a b a c h e r a n d H. S. Tobias. Iflorp. C h e m . , 7 ( 1 9 6 8 )
2471.
5 2 D. I. Nichols. d. Chum. S o c . A , ( 1 9 7 0 ) 1 2 1 6 . ANALYSIS AND APPLICATIONS O F GOLD COMPLEXES
5 3 L. G . Vaughari a n d W . A. S h r p p a r d . J An1 ('hidm. S o <c . 91 ( 1 9 6 9 ) 6 1 5 1 :
J. Organornet. Chpnt.. 2 2 ( 1 9 7 0 ) 7 3 9 .
5 4 M. 0 . F a l t c n s dnd I). A . S h u l e y , .l. C'hcrli. /'tl\'.s.. 5 3 ( 1 9 7 0 ) 3 2 4 9 .
5 5 1%. D. B d r t u n l k . W . Potrr.1. K 1.. Mosshaucr and 0 . Kaindl. %. Phgs., 2 4 0
(1 970) 1.
5 6 J . S . C h n r l t o n dn<l 1). I. N ~ c l l o l s J. . Ctlr2rrl. S o c . A . (1!)70) 1 4 8 4 .
5 7 H. Prosser. C;. Worlrnan. K. Svasst'n m d W . B. Hol/apfCL, % Phvs. 13. 24
ANALYTICAL METHODS FOR GOLD [l-3 1
(1976) 7.
58 1, P f r ~ f f c r .I<. S. Raghdvan, C'. P. Llrhterru.ilnt,r dnil K . W . Wc.st. I'hys. HPII.
IA~ll...30 ( l 9 7 , 3 ) fi.35
Many analyt~calproced~lresfor gold determmation rely on
59 .l. ,\ J. J,ir\15, A . . J I ) ~ I I I W I I .III(I l<. .l I ' L I ( I I I ~ ~ I ,l. ~ ~(:h<,m.
I ~ I ~ L Sot
, , ('III~J~. gold bemg present as [AuCl, j . Gold as the pure metal, as a
('ornrrt~trr , ( 1 9 7 3 ) :j7:i. ,\. . l o h r ~ ~ o1'~11i 1) . 'I'/?,TI.\ ~ l n ~ v t ~ r sol ft vl , ~ \ , ~ ~ r ~ ~ o , ~ l .
l !4 7 ,5
constituent of an ore, or I n many complexes can r e a d ~ l ybe
S i O P c;. . ~ I I I I < ,4 S. !vlad(lock. XI. .l X L I Y~ ~I I A ~ .I b'. WIIIIAIIIS, !\l)strarL o f converted to the requ~redtetrachloroauratc~(II1)by dmolution
lfi1/1 AI,,clir~#,. A I ~ , , ~ S /~) i~. w I I~It .~%~~~(;IYIIIII.
~ o ! ~ ~ ' ~ I I I ' P ~ S 1I, ~1 1Y~ f ~ r p o 1
o9l ,7 6 .
(;l G K a ~ n d l .K 1 , w r ~a n d N . BartIctL..I ('/IPI?I I'hys. 5:) ( 1 ! l 7 2 ) 5 0 5 0 .
in aqua ryqa. N ~ t r ~ a cc ~ dand o x ~ d e sof n ~ t r o g e nare then
l i Z K . I l u t t t ~ al n d H . F o r k l . ( ' h c n ~ th,r.. 1 0 5 ( 1 9 7 2 ) 1 6 6 4 . removed by evaporat~on,a d d i t ~ o no f m o w concentrated hydro-
.
1;3 P ' l ' d u c h n t ~ rA I I ~H . Hutt,<.l.('hi,rn 1jr.r 1 0 7 (1 9 7 4 ) 37fi I .
chlor~ca c ~ dand then further cvaporat~on.' r h ~ sprocedure IS
6 4 I<. IIutLcl. P. l'auchnt'r a n d 11. l+'orkl. ('ltc,rtt H v r 1 0 5 (1!172) 1 ..
6 5 . H. S c t r m i d h a u r . . l . K . hlnndl, C'. l*:. X r ~ z r w r L). . F . van dt'r V o n d ~ aI n d C;. P. repeated t w ~ wto ensure complete rcmoval of ox~dr.so f n ~ t r o -
v d r ~d c r K(,lr.n. .I Chc,m. S,,c , ('hvnl (i)rnrr~trrt.,(1976;) 1 7 0 .
6fi 1'. hldchrricr, M . Itvdil a n d P. Cornil, ( ' H . l m d Scl. Sc.1. ;l ,lit 21i2H ( l 9 6 6 ) 6 5 0 .
gen [l].A l t e r n a t i v e l y , d ~ s s o l u t i o nof gold by chlorme or h y d r o -
l n i ~ r g .N I I C ~('h<,rn.
. I ~ , l l . .,3 ( 1 9 6 7 ) 21 5. gen peroxide in hydroc*hlorichi m d 1 s occas~onallyused 141 . I t
6 7 F'. Mdc111ni.r. A ~ ~ ~ ~ l l l r / ' o r, .21 ~ c l(1 l 1 0 2 5 . ,l lrlore. .Vltc/ ('hc~rn , 3 0
i s , o f course, p o s s ~ b to l ~ d n a l y w gold 111 tht>form o f other
(I9fiX) 2 6 2 7 .
6 8 (;. A . E3ownrakc.r a n d R . Whiting, Arrsl J C'hc,m 2 9 ( 1 9 7 6 ) 1 4 0 7 .. complevts than [AuCl,] and examples w i l l he found I n later
(ill A. Sasane. 1'. M a t u ( ~I). , Nakdrnura a n d M . K u h o . J. .Zlnpr~.K e s o m . 4 ( 1 9 7 1 )
257.
sectmns of t h ~ chapter.s
7 0 .J. R c ~ n h o l d 11. , Z w a n ~ i g v r .1.:. H o v c r a n d C . 7,wan~igc.r.%. C h e m . . 1 4 ( 1 9 7 4 ) Another gc.neral t e c h n ~ q u e w, h l c h is w d c l y used I n analysis
3 1 4 ; H . %waii/igcr, .l. R r ~ n h o l da n d Is:. H o y r r . %. Chc.111.. 1 4 ( 1 9 7 4 ) 4 8 9 . for gold, 1s solvcwt cxtract~on.This may be used to concrntratr
7 1 .J. H r h a n . H . A . W. . I o h n s t o r ~ cn~n d H. J. PutIdc.phatt, u n p u b l i s h e d results.
.
7 2 H. Basch a n d H. B. ( i r a v . I n o r y C'hcrr~ 6 ( 1 9 6 7 ) 3 6 5 . a d l l u t e aqueous solutmn of a gold complex or to sc\parate
7 3 W . H. Mason a n d H. R . G r a v . . l A m ('hem S o c . . 9 0 ( 1 9 6 8 ) 5 7 2 1 .
7 4 11 % w a n , ~ p v r .J . R r m h o l d dnrl I.:. H o v v r . %. Chc,rn.. 1 5 ( 1 9 7 5 ) 6 9 .
gold from ~ n t r r f e r i n g~ m p u r ~ t ~Thus, e s . IIlAuCl,] may bc e x -
7 5 D. H B r o w n a n d W. F. S n u t l i . .l. ('tl(,rr~. S r c . U a l t o r ~7'mn.s.. ( 1 9 7 6 ) 8 4 8 . tracted from s o l u t ~ o nI n hydrochlor~ca c ~ dI n very high y ~ c l d
7 6 W . R. M a s o n a n d 11. H . G r a y . I n o r g C h c ~ r , ~7. . ( 1 9 6 8 ) 5 5 . by such s o l v t . n t s as d ~ e t h y ether,
l ethyi acetate, mc)thyl so-
77 .l. L. H y ~ n I, r ~ o r g .C t r ~ , m . .8 (1 9 6 9 ) 2 0 5 8 .
7 8 A . .I. M c C a f f t ~ r v P. . N S c h a L ~a n d P. .l. S t i v h e n s . .l. A m . C t ~ c , n Soc.. ~. 90 butyl ketontl, i s o - a m y l alcohol and d~chloromethane-tetra-
(19ti8) 5 7 3 0 . hydrofuran [5, 61. T h e organic phase may then he est~mated
7 9 H. Ito. J . F u j i l a a n d K. S a l t o , B ~ r l l .Chr~rn.S o c . J p r ~ . .4 0 ( 1 9 6 7 ) 2 5 8 4 .
8 0 A . K . G a n g o p a d h y a v a n d A . Chakravorty, J. Chem. P h y s . , 3 5 ( 1 9 6 1 ) 2 2 0 6 . d~rectlyby neutron actwition, atomic ahsorpt~onor spectro-
8 1 H.-11. S c h r n ~ d l k t .a n d D. G a r t h o f f , J. A m . C h e m . S o c . 8 9 ( 1 9 6 7 ) 1 3 1 7 ; W.
B e c k . W. P. Fchlharnrnc.r. P. P b l l m a n n . E.:. S c h u i r e r a n d K. Feldl, C h e m . Ber.,
photometr~cmethods 1 2, 3 , 51.
1 0 0 (1967) 2335. Gold can also be concentrated prior to analys~sby chromato-
8 2 W. H. Baddley. .'F Basolo. H. B. G r a y . C. Nolting a n d A . J . P o e , Inorg. C h e m . , graphy using an ion-exchange resm or, in a recent development,
2 (1963) 921.
8 3 A. C h a k r a v o r t y , N a t u r w i s s c n s c t ~ o f t c ~4r ~ 8,(1961) 643. a polymer~cresm containing pendant thiol groups which
8 4 W. R. Mason. J. A m . C h c m . Soc.. 9 5 ( 1 9 7 3 ) 3 5 7 3 ; 9 8 ( 1 9 7 6 ) 5 1 8 2 . selectively complex to gold [7-91. For example, a solut~on
containing gold(II1) can be chromatographed on a hexylthio-
glycollate resm. Interfermg ions such as Ag(I), Hg(I1) and BiJIII)
can then be removed by elutlon with hydrochloric a c ~ dand , which may be weighed directly [ l l , 13, 141. The derivative
fmally t h e gold is eluted w ~ t hthiorea s o l u t ~ o nas the complex of Reinecke's salt Au[Cr(NH,),(SCN),] has also been used
[Au{S C(NH,), ,l+ and estimated by spectrophotometry. [Ill.
Enrichment factors of 108-10" have been obtained by
chromatographic. methods [ 8 ] ( b ) Titrimetric methods [ l , 21
In the following s w t ~ o n as brwf mention w ~ l be l made of
the methods used for analys~so f gold in c'hemical laboratories. Most titrimetric methods for gold depend on reduction of
It would not he appropriate t o give detailed recipes here, and gold(II1) t o metallic gold. For example, hydroquinone reduces
only the o u t l ~ n of
~ s thc m ~ t h o d sw ~ l he
l given 'I'he traditional gold(II1) t o gold rapidly and quantitatively. The titration may
fire assay method of analysis of gold In ores is used only in be carried o u t using indicators such as 0-anisidine o r benzidine
spec.ialist lahoratorics and has b w n cxtrnsively rcv~c.wrdclsr- t o determine the endpoint o r by potentiometric titration.
where (101 It will thtmlfort- I-K. omi ttcd h r w Alternatively, cxc-t.ss of hydroquinonr. may bc added, and the
txcctss hack-titrated with ci~rium(1V)[l51.Mcthods bascd on
(a) G r a c ~ ~ r n c t rtncthods
w / l 11 reduction o f gold(I1I) t o gold by iron(II), titanium(III), oxa-
latc or ascorbic acid have also h e m doscribtd [l].
Most gravimctric methods for gold art1 b a s d on reduction Reduction of gold(lI1) to AuI by excess of iodide, with
of a gold-containing compound to thc. mc~taland weighing t h e titrimctric estimation o f the rel(.asrd iodine, is the basis of
gold in this form. If gold is p r r w n t as [AuCI,] , reduction another method, while clstimation o f thc cyanide uscd in
with oxalic acid, sulphur dioxidr, hydroquinone or sodium oxidation o f gold t o I A u ( C N ) , ] by air has also been used t o
nitrite is most c-ornmon, thv prvfm-rtl method depending o n determine gold.
the interfering ions present. Formaldehyde, hydrazine salts
and hypophosphorous acid arc uscd less commonly. The dis- ( c ) Spctrophotornetric methods 12,iil
advantago of this gtmeral method is that t h e gold may be
formed in a finely divided statc which adheres strongly t o tho Spectrophotometric methods are particularly useful when in-
vessel in which it is precipitated. Thus filtration and transfer sufficient sample is prcsent for the gravimetric or titrimttric
may be difficult. methods. Although intcrfrrence by other metal ions is often a
It is also possible. t o prr>cipitatcgold quantitativcrly as in- serious problem, suitahlc systems have been deve1opt:d for
soluble complexes. Thcse are often of uncertain composition analysis of gold in the presence of most of the likely impuri-
as when citarin, dimethylglyoximc o r 8-quinolinol are used as ties.
precipitants. The compounds are then filtered off and ignited The simplest method is t o convert t h e gold complex t o
t o gold metal. Other complexes are precipitated in pure form [AuCl,]- o r [AuBr,] in aqueous solution and t o measure the
and may be weighed directly. Thus stable salts of [AuCl,]- or absorbance d u e t o these ions. Many impurities interfere, how-
[ A u R r , ] are precipitated by bulky cations such as N - ( N - b r o n ~ ~ l ever, and it is usual t o extract the [AuCl,] o r [ A u B r , ] into
C-tetradecylbetainylW-tetra-decylbetain bis(trimethy1)hesil an organic solvent before measuring the absorbance. In di-
methylenediammonium or 2,4,6-triphenylpyrilium [ l , 1 1 , 1 2 1 chloromethane-tetrahydrofuran t h e species present is thought
Derivatives of sulphur-donor ligands may also be suitable. t o be [thf-H]+[AuCl,]-, while in chloroform containing tetra-
Thus thioglycollic acid, thiophenol, di-2-thienylketoxime ant1 phenylarsonium chloride t h e ion pair [Ph,As]+[AuCl,]- is
m-phenylenebis(1-tetrazoline-5-thione) all form derivatives formed 1.5, 61.
In other methods, varlous reagents can be added t o form ( d ) Electrochemical methods
coloured complexes of gold and these are then estimated spec- These methods are not often used, but ion-selective electrodes
trophotometrlcally. One popular reagent is rhodanine which
with high specificity for [AuCl,] or [Au(CN),] have recently
forms an ~ntenselyred complex with [ AuCl,]. In aqueous been developed and the method may become more popular as
solution the complex 1s formed as a colloidal suspensloll and a result [27]. The liquid ion-exchange electrode recommended
thv cwlour is unstable, but this problem can be overcome by
for [AuCl,] is based on bis(4-ethyl-3,5-dipropyl-l-pyrazoly1)-
solvent rxtract~on[ 5 ] , or by add~tionof pyr~dint,since the
methane 1271. Several ions including Zn2+and Ag' interfere.
complex 1s soluble in aqueous pyridine 1161. rhe number of
other reagents L ~ S is
C ~too n e a t to allow detailed discussion ( e ) Atornic absorption and emission spectrography
Atomic absorption spectrophotometry is becoming a partl-
cularly popular tti-hnlqut for determination of gold in trace
quantities [28, 291 Thus, using a carbon rod atomiser, concen-
trations of gold in aqueous solut~onof about 1ppm can be
estimated accurately 130, 311, and considerably lower concen-
trations can be analysed if atomic absorption 1s used In con-
junction with conccntratlon of gold by solvent extractlon or
chromatography 12). lJslng chromatographic concentration
and emission spectroscopy, concentrations of gold in sea-water
In t h region
~ of 1 0 l 2 ppm were determmed to an accuracy
of about + 10% [ 8 ] .
[AuCI4] , HCI
[huC14J , HCI ( f ) Neutron activation
[AuC:141 , IiCl
[AuC14[ , HCI This is the most scnsit~veanalytical method for gold and is
A u ( I I I ) , alkalint. the preferred technique when gold is prrwnt in very low con-
[AuCI41 , HCI
centrations as in sea-water or meteorites 14, 71. The great
sensitivity arises since ' A U is the only naturally occurring
isotope of gold and has a high ntwtron capture cross section of
[ l -3, 51, but somt. are included in Table. 11.1. Most methods 9 8 barns. The product '"AU decays by P- and y-emission with
rely on extractlon of the cwloured complexc~sInto an organic a half-l~fcof 2.7 days. Again, the gold is normally concentrated
solvent, a procedure whlch often separates gold from interfer- and separated from impurities by solvent extraction or chroma-
ing ions and which can concentrate the gold-containing species tography prior t o analysis 12, 4, 7, 32, 3 3 ) .
and thus make poss~blethe analysis of very dilute solutions of
[AuC1,]-. BIOL0C;ICAL APPLICATIONS O F G O L D [ 3 4 ]
A related method is based on ox~dationof luminol by
[AuC14]- and observation of the resultant chemiluminescence. Although gold has been administered since the earliest times
The luminescence is however suppressed by ions such as thio- for the cure of all diseases, with the aurum potabile of the
cyanate [26]. thirteenth century perhaps being the most famous cure-all, it
is only recently that a sound basis for gold chemotherapy has strong similarity between this disease and rheumatoid arthritis
emerged. The chief uses are of various gold(1) thiol corny,unds in humans. Although there is some disagreement [38], control-
in the treatment of rheumatoid arthritis and of radioactive led tests show that sodium gold(1) thiomalate does suppress
"'Au in radiotherapy. both the primary and secondary lesions of adjuvant arthritis
in rats, although it has little effect when given therapeutically
(a) Gold in the treatment of arthritis [35, 361 after arthritis has begun 139, 401.
A disadvantage of the present chrysotherapy drugs is that
The gold compounds which are presently used in the treat- they must be administered parenterally in doses of about
ment of rheumatoid arthritis are shown in Table 11.2, and their 50 mg per week, and it is difficult t o control toxic side-effects
use is generally known as chrysotherapy. Other compounds which may continue for a considerable time after chrysotherapy
such as Na,[Au(S,O,),], known as Sanocrysin, have formerly is discontinued. An orally administered drug has considerable
been used and these drugs were also used in the period 1925- advantages in this respect, and a number of trialkylphosphine-
1935 in the treatment of tuberculosis.
The gold(l) compounds are administered intramuscularly
and appear t o be as effective as any other known drug for
treatment of arthritis, though toxic side-effects are often a
Somr- Ivrtiary phosphint, compl(.xt,s o f fiold(1) with anti-arthritis propertirs
problem [37].
In the evaluation of new gold drugs, it is customary to test
if the drug suppresses adjuvant arthritis in rats, since there is a C'HLC'O,II
1 (rrf 45)
TABLE 1 1 . 2 Et$ Au S C11C02H

Commonly used gold(1) drugs


Et>
Chemical formulau Chemical name Trade name
I
S Au P,
-- p---- ---p-- , \
CII: CH,
Au--S -CHC02- ~ a + D ~ s o d ~ ugoltl(1)
I
m th~omalatr Myocrisin 1
CHL
/
CH2
(rrf 4 6 )

P' Au -S/'
I
Et2
CHIOAc
Solganol
(*c-ytpEt , (rvr 4 4 )

AcO

T h e detailed structures are n o t known. The compounds may be poly 0 Ac


meric like other complexes (RSAu),,.
gold(1) complexes have recently been shown t o suppress observation that after administration of gold drugs labelled at
adjuvant-induced arthritis in rats and t o give a high serum gold both the gold and sulphur atoms, the distribution of radio-
level. Some of the more effective reagents are shown in Table active gold and sulphur in the body is not identical [55], show-
11.3. The effectiveness depends primarily on the phosphine ing that cleavage of the gold-sulphur bond occurs in vivo. Both
ligand, with triethylphosphine being most effective, but also exchange and further co-ordination of thiolate to gold have
on the anionic group. The role of the tertiary phosphine is been demonstrated by '% n.m.r. spectroscopy, 2nd evidence
probably t o enhance the lipid solubility of the gold drug and for formation of the cluster [Au4(thiomalate),13 in the pre-
so t o facilitate its absorption and distribution in the body. sence of excess of thiomalate has been obtained [56, 571.
Also as a result of the different solubility properties, the Further evidence for the interaction of gold with thiol
distribution of gold throughout the body is different from groups is obtained by X-ray diffraction studies of crystalline
that rcwdting from administratior1 of the conventional water- proteins and enzymes containing a gold complex. The heavy
soluble gold drugs. In particular, concentration of gold in the gold atom is used to enable solution of the phase problem
kidneys with resultant harmful effects is considerably less for associated with determination of structures by X-ray methods.
the phosphine complexc~s,and it is likely that the new phos- The complex ions [Au(CN),I-, [AuCl,) and [Au14]- are
phinc-gold drugs will hc usvd thcraprutically in the not too frequently used, but it is possible that substitution of a halide
distant future. ion or reduction t o gold(1) may occur in the presence of the
protein or enzyme. Some cxamples of structures investigated
( b ) Thr. rncchanisrn of a(-tion of gold drugs by this method are given in Table 11.4, and it will be clear
that gold is often associated with the amino-acid cysteine which
Studies using rad~oac.twcly1al)tlllcd gold(1) thlomalate show contains an SH group.
that about 2070 of the gold is t..tcreted in the first two weeks, In conclusion, it is shown that gold(1) thiol derivatives can
but that after this time furtht>rcxcrction is very slow. Gold is undergo exchange with free thiols, that gold has a high tend-
concentrated in the inflamtd joints and probably acts by in-
hibiting enzymes mvolved in thc Inflammatory process \ 47, TABLE 1 1 . 4
481. Certainly, there is considerable cvldence that gold(1)
Gold d~rivativeso f rnLymrs and protcins [ 3 4 ]
thiomalate inhlb~tssuch enzymc.s as acid phosphatast,
0-glucuron~dast~, c.athepsin and glucosamine-6-phos[)hatc
synthetase and, it is suggested, that there may be a general Gold I,ibelhng agent Protr~nor enzyme Gold h~ndlngs ~ t e Ref.
effect on SH-contalnlng c3nLymcsarising through cw-ordination ---- -- --. -- --- - --

of the thlo group t o gold [49-541. Thus the inhibition may [Au(CN)21 Flavodox~n Cyste~ne
not be observed in the presence of SH protwting groups or by L~veralcohol Cyste~ne
dehydrogenase
addit~onof other SH-contaming compounds such as cysteine [AuC14]- Cytochrome c2 Histidine
or DL-peniclllamme (49, 531, which can compete successfully Lysozyme Arginine
for the gold centre. Myoglobin Histidine
For thls kind of behaviour to be observed, it 1s necessary Haemoglobin Cysteine
that gold(1) thiomalate should be able to react with more thiol Lactate dehydrogenase Cysteine
IAuI41- Myoglobin Near haem
or that exchange between CO-ordmatedR S and uncomplexed
Chymotrypsin ?
RSH should occur readlly. Exchange is demonstrated by the
ency t o bind t o sulphur-containing groups in enzymes and Gold toxicity may be treated by injection of chelating agents
proteins, and that gold(1) thiol drugs inhibit enzymes in which which hasten t,he excretion of gold from the body. Recom-
a free SH group is necessary for activity to be observed. Thus, mended for this purpose are DL-penicillamine and British anti-
the circumstantial evidence that gold therapy in arthritis lewisite (BAL), both of which contain SH groups which are
treatment is successful due to inhibition of thiol-containing particularly effective towards gold(1) [72, 741. Also recom-
enzymes which cause the inflammation is strong, and it is mended is treatment with prednisone and corticosteroids
likely that direct evidence on this matter will be sought in the generally [74, 751.
near future. Although the overall toxicity of gold(1) thioglucose is no
greater than that of the thiomalate, the former leads to con-
( c ) Other biological effects of gold siderably greater concentration of gold in the hypothalamus
of the brain [76, 771. In animal studies, this is found to result
Gold therapy may have harmful or beneficial side-effects. in obesity and hypcrphagia in mice and guinea-pigs and to brain
An example of the latter is given by the anti-histamine prop- damage in rats [76--801.
erties of gold(1) thiomalate, which is present in the therapeutic
concentration range during normal chrysotherapy treatment ( e ) Applications of rudiouctiue gold in medicine
[66]. Gold drugs also have beneficial effects against Myco-
plasma and Leishmania 1661. Radioactive "'AU finds use in medicine in radiotherapy.
Also potentially inkresting is the observation that [AuCl,]- Cold may be in the form of grains which are placed where
forms a complex with DNA probably by co-ordination of required or sometin~esin colloidal form. Colloidal '"Au is
nitrogen atoms of amino-acids 1671. This could interfere with used in radiotherapy of pleural or peritoneal effusions and
cell division and indicates that gold(II1) complcxes may be bladder cancer where an insoluble radiopharmaceutical capable
found to have anti-cancer properties. Thus the complex cis- of uniform radiation of irregular surfaces is required [81].
[PtC12(NH3),] is thought t o have anti-tumour properties due Colloidal '"Au is also used for various diagnostic purposes,
t o co-ordination of DNA t o platinum. A preliminary report for example in bone marrow scanning or in delineating the
suggests that [A~Cl~(5-diazouracil)~]*Cl does indeed have ant' lungs and liver. The colloidal gold is taken up by the organ
tumour properties [68]. It is also known that gold(1) thioma1al.1- which can then be observed by scintigraphy.
inhibits DNA synthesis in sheep lymphocytes [69]. Further
exciting progress in this area is obviously possible.
CATALYTIC PROPERTIES O F GOLI)
( d ) T o x i c i t y of gold (54, 701
Gold is generally regarded as being the least useful of the
Labelling studies have shown that gold(1) drugs are concen- nnble metals for catalytic purposes. The low catalytic activity
trated in the kidneys and, t o a lesser extent, in the thymus, of gold is due t o the d-band being filled, with the result that
liver, spleen and hypothalamus [71, 721. The precise distribu- gold is unable t o chemisorb small molecules. Thus hydrogen
tion is dependent t o some extent on the particular compounds is not adsorbed by gold a t temperatures below 473 K (above
administered. The concentration in the kidney can be particu- this temperature, thermal excitation of electrons from the
larly serious and may result in dermatitis, stomatitis, thrombo- d-band t o the 6s-band occurs) and ethylene is adsorbed only
cytopenia and renal damage [73]. weakly.
If gold is to be used as a hydrogenation catalyst, it is there- catalyst has greater specificity for isomerisation of a-pinene
fore necessary t o supply hydrogen atoms for reduction at the to P-pinene and for oxidation of ethylene to acetaldehyde
gold surface. This can be effected either electrolytically or by than has palladium alone. Interestingly, the isomerisation of
the gold-catalysed decomposition of formic acid, but neither 2-methylpentane t o 3-methylpentane occurs predominantly
method is attractive. Better results have been obtained by using by a different mechanism with a Pt catalyst than with the Pt-
very finely divided gold particles on alumina or silica supports. Au mixed catalyst, as demonstrated by labelling studies [go].
Such small metal crystallites become electron-deficient, and
their properties then resemble those of the preceding element
in the Periodic Table, so that very finely divided gold particles
take on some of the properties of platinum metal [82]. In
accord with this theory, the supported gold catalysts, which '1-Au
are usually preparcld by heating Fl[AuCl,] adsorbtd o n the
,/
adsorbed
112
support material, are able to catalyse the hydrogenation of
alkenes, alkynes and dienes under conditions where massive
gold is inactive. These catalysts also effect exchange between
deuterium gas and hydrogen atoms present in the support
material. Thus, in the catalytic hydrogenation of hutadiene,
it is suggested that butadiene is adsorbed onto the gold and is
then reduced by hydrogen atoms which migrate from the
support to the metal surface 183, 841. Exceptionally, the addition of gold t o palladium has little
Gold films prepared under ultra-high vacuum have been effect on the selrctlvity towards the catalytic isomerisat,ion or
shown to catalyse exchange between hydrogen and deuterium cracking of hydrocarbons though the reactivity is drcrcased
groups of MeSiH, and MeSiD,, apparently by reversible loss [go]. Addition of gold t o rhenium enhances the catalytic
of H, or D, from the chemisorbed molecules with formation properties, for cxample in the conversion of C,, hydrocarbons
of chemisorbed MeSiH or MeSiD species [85]. Gold is also a to benzene 1911.
catalyst for isomerisation and hydrocracking of hydrocarbons, Gold compounds may also have catalytic properties, either
but is less effective than other noble metals. One interesting alone or in conjunction with a scxond transition metal com-
example is the catalysis of the isomerisation of the complex pound. For example, the manufacture of vinyl acetate from
strained-ring molecule diademane to snoutene and then t o ethylene, oxygen and acetic acid is catalysed by palladium
basketene by gold [86]. Some reactions of oxygen are also acetate on silica or alumina promoted by EI[AuCl,] or, prefer-
catalysed by gold, for example the oxidation of propene t o ably BaAu,(OAc), [92].
propene oxide and of methanol t o formaldehyde [87]. Some catalytic reactions are based on the oxidising ability
Gold is also frequently used t o modify the catalytic of gold(II1) complexes. For example, acetylene is oxidised to
properties of another metal [88]. Often, gold decreases the glyoxal in water-acetonitrile by [AuCl,(YPh,)].
reactivity but increases the specificity of the catalytic reaction
For example, addition of gold t o platinum or iridium surfaces HCCH + 2[AuCl,(PPh,)] + 2 H 2 0+CI10. CH0 + 2[AuC1(PPh3)]
gives increased selectivity t o the isomerisation of iso-butane
rather than t o its hydrogenolysis [89], and a gold-palladium
Since [AuCl(PPh,)] can be oxidised back to [AuCl,(PPh,)l by of [Au(CN),]- occur [102]. Gold is also used t o connect com-
chlorine or tetrachloro-o-quinone, the system can be made ponents in micro-electronic circuits. For this use, various gold
catalytic and yields of 250% based on gold have been obtained pastes may be used, or gold may be deposited by the metal
[93]. Primary amines are also oxidised t o ketones or aldehydes sputtering technique from the vapour phase. The technology
by gold(II1) complexes [94], and alkenes can be converted t o involved in the various uses of gold in electronics is now
epoxides by [AuCl(PPh,) 1 and 0 apparently by a free-radical extremely sophisticated, with the need t o use the minimum
mechanism [95, 961, but none of these systems is yet attractivv quantities of gold being a particularly important factor.
commercially. Gold(II1) complexes can also be used stoichio- Gold is also used t o decorate glass and ceramics. Here,
metrically for the oxidation of alkenes, alkynes and cyclo- another technique for producing thin, strongly adhering gold
propanes [96b]. Cyclopropanes are first isomerised t o alkenes coatings is t o adsorb a solution of a gold compound onto the
which then g i k 1,2-adducts. Other catalytic. reactions are the surface and then to pyrolyse the compound t o gold. Recom-
hydrogenation of alkencs with AIL(III)-S~bonded complexes mended for this purpose are such compounds as gold(1) thio-
[97], the dimerisation of acrylonitrile to adiponitrile using lates and phosphine complexes of gold(1) [103, 1041. Where
[AuBr(PMe,)l and sodium amalgam [98 1, the metathesis of particular designs are required the "liquid gold" solutions can
alkenes using [AuCl(YPh,)] and organoaluminium cwmpounds be painted onto the pottery or glassware.
[99] and the decomposition o f diazoalkanes by [AuC13(pyri-
dine)] [ l o o ] . The catalysis of conversion of isocyanides t o OTHER APPLICATIONS OF GOLD
formamidines was discussed in Chapter 7.
In conclusion, neither gold nor gold complexes have been Applications of gold which do not primarily involve its
used cxtrnsivcly as catalysts in t h past
~ but rvcrmt research chemical properties will be reviewed only very briefly. The
suggests that their use is likely t o increase in thc? future. chief uses are as a monetary standard, in jewellery and in
dentistry. The infrared reflectivity of gold leads t o its use in
the aeronautics and space industries, and its low chemical
METHODS O F GOLL) COATING reactivity leads t o use in lining specialised chemical plant and,
alloyed with platinum, in the production of viscose rayon. It
One of the most rapidly expanding uses of gold is in the is encouraging t o the chemist that the fastest growing uses of
electronics industry. Gold is used in switching devices and in gold are in industrial rather than decorative applications
micro-electronic circuits. For thcse purposes, gold is usually [105].
plated onto another material electrolytically. The nature of
the gold deposited is critically dependent on the nature of the
electrolyte solution used. Most such solutions are based on
REFERENCES
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1973.
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F. .l. M. J . Maesserr. 1.'. I). Posrna a n d J. Balko. A~lul.(~hc~rn.. 4 6 ( 1 9 7 4 ) 1445. fi7 C. K. S. P i l l s ~a n d 11. S. N a n d ~ ,I l ~ o p ~ ~ l v m clr1s .( 1 9 7 3 ) 1431 : ,l. Kollman,
K. Dittrich a n d W. Mothrs. 7'alanla. 2 2 (1 9 7 5 ) 31 8. C. S c h r o c t r r .rnd K . 1Ioyc.r. .l 1'rol:l C h v n . . 31 7 ( 1 9 7 5 ) 51 5.
H. W. Hunrmrl, Analyst. 8 2 ( 1 9 5 7 ) 4 8 3 . f i 8 C. 1)ragulrscu. J. Heller, A . Maurrr. S. P(~licec.V. Topcut. M. Cs:~lct. S. K ~ r r h n r r ,
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1). 'L'. Wall. M. .I. DI Martlno a n d H. M. S u t t o n . M c d ('hcrn . Scr. Monopr.. 6 9 R. N. P. Cahill, l c . \ , ) ~ ~ r . i r ~ ~ < 27~ r(1 ~ 1~ ). 9 1 3.
t l9r 7
1 3 ( 1 9 7 4 ) 2 0 9 : 1'. Y. S h r n , ibid., 1). 179. 7 0 11. C . 11~1dgr.I,. .I. Lrach, I.'. A. Snrlth. W. H . Stralrr a n d I). R. Taves, I)rill's
M. .I. 1,rfevrc. Kctr. I{t,lyc, f i ~ ~ n ~ ~ ~ ~ 2o6p( u1 9f 7l 4~) .75. . I'har-nluc~r~l ,Mr,d. MrGr.~w-I11ll.Nvw York, 4 t h erl., 1 9 7 1 . p. I 1 20.
T. .I. Constable. A. P. Crockson. It. A . Crockson a n d B. McConkev, The, Lance1 71 If. I,. Atkins, I t . M. I i ~ n ~ b r t ~A. h tP. , W<)lf,A. N. Ansari dnd M. ( ; u ~ l l a u m c ~ .
(1 9 7 5 ) 1 1 76: R . H. I'rc.vbc~rg, In .I. I,. Hollander (Ed.). A rlhritis a n d Allied /<~ldlO~l~ 11~5) .(.1 9 7 6 ) 723.
('~1r1dr1rorr.s. Lea a n d I * ' r b ~ g r rPhilade1l)hia.
. 1966. 7 2 M. R u t ~ ~ A n .. Sliw~irskl.M. Phollas. M. F'c~ldlnana n d N. %vaiflc.r. I'r-oc Soc.
1. I). .Itwmp a n d 11. L. F. Currrv. Allft. lihc2~rfn. 1);s.. 27 (1 9 6 8 ) 577. I..'.xr). 1l1o1. ;ll<t~l.. 1 2 1 ( 1 9fi7) 290.
D. T. Wall, M. .I. Di M a r t i l ~ oa n d A. M ~ s h e r AIIII., H h e u n ~ .Dis.. 3 0 (1 9 7 1 ) 7 3 N. 0. Hothernrich. V . K . Philips. W. R t ~ g r na n d M. 11. T h o n ~ a s Arlhrrtrs , Khc.um.,
303. 1 9 (1976;) 1 3 2 1 .
R. D. S o f i a a n d .l. F. Douglas, A y ~ t l t sAclror~s.3 ( 1 9 7 3 ) 335. 74 1). F. Hill, ,71<zd('/I,, Nor111 .A m , , 5 2 ( 1 9 6 8 ) 733.
D. T. Walr. M. J . Di Martino, B. S u t t o n a n d A. Misher, J. f'harmwol. E:xp. 7 5 B. lltmm. K . M.rsi. M. Wvkslc>ra n d R . I,. Nn<.hntan, Arch. l n l ~ r f r .hlc~d..1 3 4
'/'her., 1 8 1 ( 1 9 7 2 ) 292. (1974) 1012.
B. M. S u t t o n , D. T. Wall and .l. W n n s t o r k . Ger. Pat.. 2.434.920. Feb. 1 9 7 5 ; 76 A. 1.:. I k b u n s . I,. Stlvt.r, k.. P. Cronkttv. H. A. .Johnson. G. Brvrhrr. 11. T e n l e r
Chcm. Abslr., 8 3 ( 1 9 7 5 ) 8 4 8 5 7 . m d I. L. Schwart,. ,\rn J I'I~ys~ol.. 2 0 2 ( 1 9 6 2 ) 713.
B. M. S u t t o n , E. MeGustv, D. T. Wali. a n d M. J. d i Martino, J. M1.d. Chcm., 7 7 A E:. I k b o n s . 1. K r ~ n ~ s k A. v . 14'roma n d H. .I. C l o u t ~ e r ., A m J I'hv.si~)l., 2 1 9
1 5 ( 1 9 7 2 ) 1095. (1970) 1403.
D. T. W a l ~ M. , J. d i Martino. W. L. Chakrin, B. M. S u t t o n a n d A . Misher. 7 8 R. J. Chana a n d R . H. Perscllm. I'r~r<.Soc. E x p R ~ o l .M d . . 1 2 9 ( 1 9 6 8 ) 568.
J. Pharmacol. Esp. 7'her.. 1 9 7 ( 1 9 7 6 ) 1 4 5 . 7 9 P. d c Lacy. C. Dent, A. C. T e n v a n d E. H. Q u ~ n n Arch. . l n t Pharmacodvn.
E. R. McGusty a n d B. M. S u t t o n , U.S. Pat., 3,718.679 a n d 3,718.680; Chem. Thr9r.. 21 1 ( 1 9 7 4 ) 3 4 1 .
Abstr.. 7 8 ( 1 9 7 3 ) 1 3 5 6 7 2 a n d 1 3 5 6 7 3 . 8 0 R. B. Sandrew a n d J. Maycr. I'hysiol. l i f ~ h a ~1~0. .(1 9 7 3 ) 1 0 6 1 .
8 1 E. E. R o g o f f . R. R o m a n o a n d E. W. Hahn. H a d l o l o ~ y ,1 1 4 ( 1 9 7 5 ) 225. APPKNDIX
8 2 G. C. Bond a n d P. A. Sermon, Gold Bull., 6 ( 1 9 7 3 ) 102. G. C. Bond, Gold
mu.. 5 (1972) 11.
8 3 G. C. Bond, P. A. S e r m o n , G. Wehh, D. A. Burharian a n d P. B. Wells. J. Chc,nt
Soc.. Chem. Commun., ( 1 9 7 3 ) 444.
8 4 D. A. Buchanan a n d G. Webb, J Chcm Soc.. Faraday 7'rans. I, 71 (1975)
GOLD-ELEMENT BOND LENGTHSa
134.
R5 D. 1. Bradshaw. R.B. Moyes a n d P. B. Wells, J Chf2m.S o c , Chr7m. C o m m u n .
(1975) 137.
8 6 L. U. Meyer a n d A. d e Meijere. 7'ctrahrriron I ~ t t (.1 9 7 6 ) 497.
8 7 C. N. Hodges a n d L. C. Roselaar. J Appl. Chvm. Hiotcchnol., 2 5 ( 1 9 7 5 ) 609.
A. GOLD-HALOGEN BOND LENGTHS
8 8 E. G. Allison a n d G. C. Rond. (:alal. KPO.. 7 ( l 972) 233.
8 9 D. 1. Hagen a n d G. A. Sornorjai, J ('otol.. 41 ( 1 9 7 6 ) 466.
9 0 A. O'Cinnride a n d F. G . Gault. J . ('ulal.. 37 (1975) 311.
91 J. K. A. Clarkr a n d J. F . Taylor. J Chcm S o c . E'aradov Trans. I. 71 ( 1 9 7 5 ) Compound r(AuX)/pm Comments Ref.
2063.
9 2 H. F e r n h o b , F. Wunder a n d H. .l. S c h m d t . Ger Pat., 2,087,087, 1972: C'hcrn
,\hstr.. 77 (1 9 7 2 ) 8 7 8 9 7 : S. S c h ~ , t t .D. W. Lum drld I. I,. Mador. (:rr Pat.. terminal A u F distance 1
2.420.374. 1 9 7 4 : ('hcm ,A hstr.. 8 2 ( 1 9 7 5 ) 90f559. bridging A u F distance
9 3 K. A. C. Rrnnle. Brit. Pal.. 1.071.YO2, 1 9 6 7 ; Chcm. Abstr.. 6 7 ( 1 9 6 7 ) 5 3 6 8 5
2
94 M. E. Kuchne a n d T . C. Hall, .I. Org. ('hvrn.. 4 1 ( 1 9 7 6 ) 2742.
9 5 A. Fusi, K. U g o . b'. Fox. A . Paslni a n d S. Ccnlnl. d O r g a n o m ~ t .('hc,m., 26 hridging AuCl 3
( 1 9 7 1 ) 417. bridging A u ( 1 b C I 4
96 K. Masada a n d A. Y a w l , .lapan I'af.. 71 09.69 1. 197 l : ( ~ h c r nA hatr.. 7 5 hridging A u ( I I I b - C l
(1971) 19786. terminal A u ( I I 1 F C I
( b ) R. 0. C. Norman. W. .I. E. Parr a n d C. H. Thonias. J (Ihrm. Soc.. Prrkirl
'I'rans. 1. ( 1 9 7 6 ) 1983. hridging Au(III)--Cl 5
97 M. C. Muller. Gold Hull.. 7 ( 1 9 7 4 ) 39. terminal Au(ll1)- Cl
9 8 K. Y a m a m o t o a n d M. Kawaniata. J a p a n 1'01.. 71 16.730. 1 9 7 1 : ('h6.m. Abstr in [AuC12j- 6
7 5 ( 1 9 7 1 ) 64570. in [AuCI4]-
99 D. H. Kubicek a n d E. A. Zuech, [!.S. Pnt., 3.558.520. 1 9 7 1 : C h r m . Abstr..
74 ( 1 9 7 1 ) 99441. 7
1 0 0 M. G. Krakovyak a n d S. S. Skorokhodov. Vysokomol S o ~ d i n . Scv. . A., 1 1 8
( 1 9 6 9 ) 794. 8b
1 0 1 R. T. Page, M u l Fintxh. J . , 2 0 (1974) 87 a n d 122. 9
1 0 2 .I. A. Harrison a n d J. T h o m p s o n . k'lrctrochrm. Acla.. l 8 ( 1 9 7 3 ) 829.
1 0 3 H. M. Fitch. 1 3 ~ 1Pal., ~. 6 2 1 , 886, 1973. 9b
104 l?. M. P o t r a f k r , IJ.S. Pat.. 3.625.755, 1 9 7 1 : (Ihrjm. Ahstr.. 76 ( 1 9 7 2 ) 62691 trigonal planar,
1 0 5 1). Lloyd-Jacnb. Gold Ijull.. 4 ( 1 9 7 1 ) 25. LCIAUP = 1 18.7' 10
[AuCI(P- P)] three-CO-ord.gold(1)
I C I A u P = 90.4,
93.4' ll
12
13
trans t o C1 14
trans t o PPh,
trans t o CbFS 15
trans t o SPr2 16
trans t o Ph
distorted square 17
pyramid, t r a m to
C1
trans t o N
" F o r abbreviations, see p. 266.
APPENDIX A--continued

Compound r(AuX)lpm Comments Ref.


Compound r (AuX)/pm Comments Rrl. P

distorted square 18 r(AuS) 32


pyrarmd, t r a t ~ st o 33
CI S-bonded sulphite 34
lruns t o N 9
distorted square 19 trigonal gold(1) 35
pyramid, axial 16
Au--Cl asymmetrically bonded 36
gold(I1) complex 20 dithwcarbamate
r(AuBr) 2l 37
22 38
45 39
t e r m ~ n a lAuBr (listancc 7 1 40
brdgrng AuBr lruns t o 21
Br bidentate dithio- 4l
hridg~ngAuBr lrut~.\t o carbamate
Me monodentate d i t h ~ o -
trutls t o P and C 23 carbam,~tc,
AuS(d~thiocarham,itc.) 4 2
l r i ~ n st o P 2:$ AuS(mn1)
lrans t o C AuS(dith~ocarbamate) 4 3
distorted square lH AuS(mn t )
pyramid, trans t o 44
Br br~dgingA u S t 45
tram to N r ( A u T t ) calavtrite 46
bridging iodide 24 r ( A u T c ) In k r e n n e r ~ t e 4 6
tetragonal gold(II1) 25
cluster complex 26
gold(I1) complex 27 C. (;OLD--GROUP VB ELEMENT BOND LEN(:THS
carbene complex 2H
Compound r (AuX)ipm Comments Ref.
-
~--p--p

B. GOLD-GROUP VIB ELEMENT BOND LENGTHS [ A U ( C C P ~('P~NH,)]


) 203 47
[AuCl(piperidine)l 206.8 8b
[ A u ( ~ ~ )(PPh.dl
PY [PFd 21 6.6, 221.2 distorted-trigonal 48
Compound r (AuX)lpm Comments RVI gold(J)
[ A U ( N H J ) ~[No31
] 3 202 49
[ e n ~ ~ l ~ [ ~ u ( ~ 0 3 12-
)2(en) 211.9, 213.3 34
[AuC1(Ph4porph )] 200 av. square-pyramidal 19
gold(II1)
[ { A ~ ( c P ~ = c P ~ c P ~ & P ~ ) o H } ~ ] 223,226 bridging AuO 31 [AuC13(2,9-dimethylphen)] 209 t r a m t o C1 18
APPENDIX C conlmued D. G O L I t C A R B O N BOND LENGTHS

Re1 ---
Compound r(AuX)/pm Comments
Compound r(AuX)lpm Comments Ref
258 axial position of square
pyramid [Au(CN)zI- 21 2
[AuBr3(2,9-dimethylphen)] 208 trans to Br 18 [Au(CN )(PPh3)1 185
261 -
axial nitrogen [Au(CN)(MeNC)] 201 r (AuCN)
r ( AuCNMe)
lrans t o Cl
axial nitrogen

bridging carbon

r(AuMe) truns ylid


r(AuMe) lrans Me
r.(AuCH2)
t r a t ~ st o P
trarls to Me
lruns to C1
lrrrns to P

238.2
221.2
232.3
227.5, 228.3
227
230.7, 231 .O
229 Au(1kP 23
230 Au(1IIkP Au(IkC 60
221-229 cluster complex Au(IIIFC(CF3)
2 30 cluster complex Au(II1F-Me
227.4-231.1 cluster complex carbene complex 28
233.5 gold(I1) complex 20
250 gold(I1) complex 27
235 mean value 66
237 mean value 66
69
tetrazolato complex 70
71
266

E. GOLD-METAL BOND LENGTHS

Compound Comments 1 F. M. H IElnsteln. P. K. R a o , d. T r o t t e r a n d N . Bartlett. J . ('hc~rn.S o c .a. ( I g ( i 7 )


478.
Au cubic close packed 2 A .l. E i l u d r d s a n d G. R. J ( ~ n e s J. . Chc,m S o c . A ( 1 9 6 9 ) 1 9 3 6 .
3 F:. \l. \V . I a ~ i s s r n ..l. C . W F o l r n r r a n d G. A . h ' l r g ~ w .J 1 . c (~' o r n m o u .ll,st..
Au2 gas phase only 3 8 ( 1 9 7 4 ) 71.
[{Au(S~CNP~?)}~] r ( A u A u ) intra- 4 D. H. Dell',41nlco, F. C a l d e r a / / o . F. h l a r c h e t t ~ .S. Mvrlinu a n d G. Perego,
molecular .I. ('111.m Soc.. ('hem. C ~ ~ m r n u r( ~1 9. ,7 7 ) : < l .
r ( A u A u ) inter- 5 E. S. Clark. D. H. T e r n p l r t o n a n d C. hl. M r G ~ l l a v r y ..4cla C ' r ~ s t a l l ( ~ p r1. .1
(I 9 5 8 1 2 8 4 .
molecular S J C. M. T. Eijndho>c.ri a n d G.C. Vcrschuor. .\lulc~r.l i c ~ s l$uii.. 9 ( 1 9 7 4 ) 1 6 6 7 .
r(AuAu) 7 N . C Barntiger. E. Hc.n!i<.tta n d I). hl. S o b o r o f f . Ac.tn C'?-vstullrrgr., B 3 2
r(AuAu) (1976) 962.
J-( AuFc) R Cr. .I Arai. K,,,.7 ' 1 1 1 , . ( ' J I I ~ I'uvs l l m 81 ( 1 9 6 2 ) 3 0 7 .
:b) .l. .I. G u k . P. G. . I o n c a . hl. .I. Mdvs d n d G . 51. S h c l i l r ~ c k .J . ('ti(,nl. Soc..
D a l t o r ~ I'rarls., ( 1 9 7 7 ) 8 .
9 ( a ) M. G. B. 1)rew ,incl M. ,I. I<lt.dl. .I. ( ' l i ~ ~ mSo<,.. 1lrilto11 T'rans.. ( 1 9 7 3 ) 5 2 .
(h) H. S c h ~ n l d b a u r .A. W o h l l c l ~ t ~ nF.. Wagnt,r. 0.O r a m d a n d G. I i u t t n c r . C'hvm
Rev., 1 1 0 ( 1 9 7 7 ) 1718.
1 0 N. C. Harn/~gc.r,K M . I)ittc,n~c~rv d n d .l. K . I)ovlc.. Irlorc Chc,rn., 1 3 (1 9 7 4 )
hlran centre to peri- 805.
phery 1 1 M. Bnrrow, 11. B. Bu~.rgl. D. K . .Johncon a n d I,. M. V r n a n ~ i J. . Art1 ( ' I I ~ ~ JS(J<,., II
Mean r ( AuB) 9 8 (1 9 7 6 ) 2.3.56.
1 2 P. G. J o n c s . .l. J. G u v dnrl G M . S h e l d r ~ c k ;, I ~ . l u( ' r \ . \ l a l l o ~ . r - B31
.. (1975)
Mean r ( A u B ) 2687.
r(AuW\ n ~ A . L,. K o d ~ c . r s .. Z I . / O ('r\,slulloirr.. B31 (1 9 7 5 )
1.3 M . R ( ' s l r ; ~ ,l.. R . N a s s ~ r n h t ~dnd
r (Auhln) 1112.
r(AuW) 1 4 G. Bandoll. I). A . Clt31nentr. G . M a r a n g o n ~a n d L. Cattallni. J ('hr>m. S o c .
U a l t o t ~Y'rans., ( 1 9 7 3 ) 8 8 6 .
r ( AuCo) 1 5 R. W. Bdker a n d P. .I. Paulirlg. J. C/ilfnl S o c . ('hcnl ~ ' o l l l r l l u ~ l(]!)Ci'J) .. 745.
1 6 M. McPartliri a n d A. ,I. Markwrll. J O r y a f ~ o n ~ oC'h<'rn.. t. 57 ( 1 9 7 3 ) C25.
1 7 K. J. C h a r l t o n . C. M. fIarris. H. I'atil d n d N. C . S t c p h c n s o n . I r ~ o r g .Yucl Ct1c.m
1,r~ft..2 ( l 9 6 6 ) 4 0 9 .
ABBREVIATIONS .
1 8 W . T . Rohlrison a n d l.:. SIIUI..I C'hc.~rl S f j c , 1)uiton 7'rufls ( 1 9 7 5 ) 7 2 f j .
1 9 K. T ~ n i k o v l c hd n d A. Tulmskv. I r ~ o r ~( ,.' I I I ~ ~ 1I .6. ( 1 9 7 7 ) 9 6 2 .
, K . Mancll. A . Frdnk a n d G. H u t t n r r . ('hc2m H<,!-..1 0 9 ( 1 9 7 6 )
2 0 If. S r h n i ~ d b a u r .l.
466.
B~PY = 2,2'-bipyridine
2 1 P. T. Reurskrns. H. .I. A. Bladuw. .J. A . Crdb d n d .l. .l. Steggerda. I n o r g C'hern..
Bu = butyl
7 (196 8 ) 805.
Diars = 1,2-bis(dimethy1arsino)benzene 2 2 F. W. B. E ~ n s t e l na n d I t . K c s t ~ v o .4cla
, ('ry.slallo~.r.. B31 ( 1 9 7 5 ) 6 2 4 .
2,9-Dimethylphen = 2,9-dimethyl-1,lO-phenanthroline 2 3 M. A. B m n r t t , K . IIoskms, W. R. K n e e n . R . S. N v h o l m . P. R. H l t r h c o c k ,
En = 1,2-diaminoethane R. Mason. G. B. K o b r r t s o n a n d A . D. C. Towl. d A r r ~ ('hcrn Soc.. 9 3 (1 9 7 1 )
4591.
Et = ethyl
2 4 A. W e ~ s sd n d A . W<.iss,% R'alurfi~rsch.. 1 1 b ( l 9 5 6 ) 6 0 4 : N. J a g o d ; l ~ n s k i .
Me = methyl %. Krhsl.. 1 1 2 ( 1 9 5 9 ) 8 0 .
P-P = 2,11-his(diphenylphosphinometh> 2 5 V. F. D u c k w o r t h a n d N. C . S t c p h c r i s o r ~ .Irr<~rg.( ' h c ~ n ~8. . (1 9 6 9 ) 1 6 6 1 .
phenanthrene 2 6 P. Bellon, M. M a n a s s r r o a n d M. Sdnsonl. J. C h e m . S o c . . D a l t o n I'runs.. ( 1 9 7 2 )
1481.
Ph = phenyl 2 7 .l. P. Fackler. Jr., persondl c o m m u n i c a t i o n .
Ph4porph = cu,o,y,&-tetraphenylporphinate 2 8 Lj. Manojlovlc-Muir, J. Or-pattorn1,1. Chcjni.. 7 3 ( 1 9 7 4 ) C 4 5 .
Pr = propyl 2 9 C. D. G a r n e r a n d S. C. Wallwork, J. C'hran~.S o c A , ( 1 9 7 0 ) 3 0 9 2 .
TCNQ = 7,7,8,8-tetracyanoquinodimethane 3 0 G. E. Glass, .l. H. K o n n e r t . M. G. Milrs. D. B r i t t o n a n d K. S. Tobias. J A m .
C h c m . Soc.. 9 0 ( 1 9 6 8 ) 1 1 3 1 .
31 M. P e t v a u - B o ~ s d c n g h ~ r n.I.. Mrunler-Plrct nnd M. van Mt,ersche. Crysl. Struct. 6 8 M. M<.Partlui. R. Mason a n d L. Malatesta. J. Chcm. Soc.. ( ' h ~ m C o m f r ~ l ~. t !
C'<~mnlun.. 4 (1 9 7 5 ) 375. ( 1 9 6 9 ) 334.
3 2 11. liuben, A. Zalkln. M. 0. I~'al1ensdnd I ) H . Tt'mpleton. Inijrg Chcm.. 1 3 a n R . K . Kvan. Acta Crystallogr.. B28 ( 1 9 7 2 ) 1 6 2 9 .
6 9 R . A . P ~ n r i < ~ m*rid
(1974) 1836. 7 0 W. P. Fehlhammer a n d L. F. Dahl. J. A m . Chem. Soc.. 9 4 ( 1 9 7 2 ) 3 3 7 0 .
3 3 P. G. .l~)ncs..l. .l. (;uv a n d G . M. S h e l d r ~ c k .l c t u C'rvstulloyr., A32 ( 1 9 7 6 ) 3 3 2 1 . 71 S. K < , m ~ v aJ., C. H u f f m a n a n d J. K. Kochl, Inorp. Chem., 1 6 ( 1 9 7 7 ) 1 2 5 3 .
3 4 A. n u n a n d arid I t . ( i r r d ~ l ,:lclu ( ' r ~ s l o l l o i l..~ B31 . (1!)75) 370.
3 5 J. C. Huffnian, K S. Koi.h and A. K . S ~ e d l r .I. 9 m ('hr7m Soc.. 9 8 ( 1 9 7 6 )
4340.
36 .l. G. Wilnhovcn, i V . P. .I. 11. Bosnlan a n d P. ?' Bcurskrns. J ('r?st Mlr~l.SLruct.,
2 ( 1 9 7 2 ) 7.
:17 R. Hess,, dnti P . I t . n ~ ~ ~ s ( . .hI vr ,10 C/rr,m Scarrd.. 26 1 1 9 7 2 ) 3855.
38 S. L. I,dwL<,ll, 1V . l , f t < , h r b a ~ r gnn(l h (; I'. K o k o t n ~ l o /,!oi-g . ('hfam.. 11 ( 1 9 7 2 )
2227.
3 9 P. 'S. Brur5kcris. .l. A ('m> .rntl ,l c;. M wrl dt.r I,lr~dt.r~. I I ~ ~ I ~ ('hr7m..
I,* 9 (1 9 7 0 )
475.
4 0 J . A. ( : r f t h , . l . ki. t \ < ) o r c l ~ P.
k ~ l' t3i,ursk<,11h ~ I I C AI M Vvrh~><,vvn, ,l Crvsl. MiiL
S l r u c l , 1 ( 1 9 7 1 l 155.
.
41 , l . H. X o < > r ( l ~r k,,v s / . , S i r t ~i< 1 ' , 1 t n t 1 c u r t 2 (197:i) 81
4 2 .l H. N < ) o r d ~ k'l'. \L' I I t i n ~ t r ~ t ~ ,in(l l ~ n k.I. (;. M i-d!i (let Llnrlrti, d ( ' o r ) r r l C hem..
2 (1973) 185.
4 3 .l. H. Noorritk a n d P. 'I' Br'urskrsm. .l ( ' r v s l %l01 5irlc(~I..1 ( 1 9 7 1 ) 339.
4.3 ,l. H. F:ric~~~~:irk ~ I I ( ,l.
I A . Ihi,rs, 1 1 1 o f y ( ' / I , , I ~ I . . 7 ( l 9 f i 8 ) 2f;.'j(i.
2 5 D. Mc,ot,. A. t<,~l)<~nt.au. H. Wu~id<.rllch a n d (;. Kost.nati.11r. .I S ~ l t d Stutc C h r m . .
6 ( 1 9 7 3 ) 583.
4 6 R. W. C.; Wvck<)ff.('r\~,slolSlrucliir-es. Vol. I . I n t c r s c ~ r ~ ~Nt3w c e , York, 2nd ed.,
1 9 6 3 , IJ. 337.
4 7 P. W. R. C o r f ~ v l dand H. M. M. St1var1.r. Acla ('rv.~tullogr..2 3 ( 1 9 6 7 ) 156.
4 8 W. C l e ~ g Acts . ('rvslollo~l-..B 3 2 (1 9 7 6 ) 271 2.
4 9 M . Weishaupt a n d .l Stra(.hl<l./ r l ~ ~ t ~ r f o R:jl . ~ w l( 1~9 7 6 ) 5 5 4
50 P. L. Bellon. M. Manasst%r<~ arid M. Sanscln~,KIC Scl., 3 9 ( 1 9 6 9 ) 1 7 3 .
( b ) S. Esprras. Acla ('h6.m Scund.. A30 ( 1 9 7 6 ) 527.
51 P. D. Gdvens. J . .I. Guv. M. .I. Mdvs , ~ n dC;. h1. S h c l d r ~ c k ,jiclo ('rvslullopr.,
B33 ( 1 9 7 7 ) 1 3 7 .
5 2 K. W. Bakrr a n d P. .l. Pauling. J ( ' h c r ~ S<,c.. I)ullor~ 'I'rut~s.,( 1 9 7 2 ) 2264.
5 3 C. .I. Gilmorc a n d 1'. Wc,odward, d. ('hczm Sot , ( ' h ~ m Commut? . . (1971) 1233.
54 .l. J. Guv. P. G. Jnnt.s and Ci. M. S h r l d r ~ c k .lr.lu . Crvstallog~..,8 3 2 ( 1 9 7 6 )
1973
5 5 T. I,. Blundell a n d 11. M. Powc~ll,J C'/~c,ni S ( J ~A. . ( 1 9 7 1 ) 1 6 8 5 .
5 6 K. '4.. I. F. M'rnndn, Aclu Crvslollogr.. 2 3 ( 1 9 6 7 ) 6 4 9 .
57 .l. B. W ~ l f o r dm d 1%.M. Powell. J C'hcm. Soc A , ( 1 9 6 9 ) 8.
5 8 1,. .I. Guggenberger. J Orparlomr~t.Chvrn.. 8 1 ( 1 9 7 4 ) 271.
5 9 V. C;. A n d r ~ a n o v Yu. , 'S. Struchkov and E. K. Itc~sslnskava.J. Chem. Soc.,
C11r.m C u r n m u t ~ . .( 1 9 7 3 ) 338.
6 0 J . A. J . Jarvis, A. Johnson a n d K . .I. Puddephntt. J Chcm. SIIC..Chum. C o m m u n .
( 1 9 7 3 ) 373.
6 1 P. L. Bellon, F. C n r ~ a t i .M. Manassero, I,. Naldml a n d M. Sdnsoni. J Chem. Soc..
Chcjm. C o m m u n . , ( 1 9 7 1 ) 1 4 2 3 .
6 2 P. I,. Bellon. M. Manassero a n d hl. Sansonl, d Chvm. S o c 1)alton 'I'rans.. .
( 1 9 7 3 ) 2423.
6 3 M. F. P e r u t ~a n d U. Welsz. J. Chcw Soc.. ( 1 9 4 6 ) 438.
6 4 A . Rosrnzweil: a n d D. T. Cromer, Acta Cryslullog~. .. 1 2 ( 1 9 5 9 ) 709.
6 5 .l. P. Fackler, Jr., and C. P a p a r ~ / o s ,J. Am. Clif~tfr.Soc., 9 9 ( 1 9 7 7 ) 2363.
6 6 H. M. Colqhoun. T. .J. Greenhough a n d M. G. H. Wallbridge, J Chem. Soc.,
Chrm. Commun., (1976) 1019.
6 7 V. G. Albano. P. L. Bellon. M. Manassero a n d M. Sansoni. J. Chem. Soc., Chem.
Commun., (1970) 1210.
Cat~siunr,cur,~te-(I ) 3b -, vibrational sprctra 221 - 2 2 2
('arbvnc~complexes 144-148 Dialkylgold halides 1 2 6 1 2 7
~u)nicI \ l 4 4 14-5 Dialkylselenide complexes
C a b o n \ Is 1 0 , 4 3 -, gold(1) 6 0
Carboranrb complexes 166-167 -, gold(II1) 8 6
, goltl(l1) 72 Dialkylsulphide complexes
Catalys~s253-256 -, gold(1) 60, 64
Charge transfer spectra 237-239 -, gold(II1) 8 6 , 1 3 2
Chem~lum~nescence246 -, vibrational spectra 217, 219
SUBJECT INDEX C h l o r ~ d ec o m p ! ~ x e s 11,2-Diaminoethanecomplexes of
, gold(1) 65 gold(II1) 77
, gold(II1) 9 1 Diazouracil complexes 252
-- , , substltutlon reactions Dibenzylsulphide complexes 6 9 ,
181-184 72
Acetate complexes, gold([) '19 , gold( l ) 5 2 - , stretching force constants -, gold(II1) 1 8 8
Acety iacetonatogoltl c o m p l c x e ~ - gold(1II) 81, 1 3 4 2 1 1 - 2 1 3 , 218 , n.m.r. spectra 225
101, 192 A r t h r l t ~ streatment 2 4 8 2 . 5 2 Chlorine wlth gold 3 3 Diethylenctriamine complexes of
Alhene complexes 148 151 Arylgold complexes 1 0 1 Chromatography 243, 247 gold(II1) 7 8 , 1 8 2
Alkene oxldatlon 256 , vrbratlonal spectra 221 Chrysotherap) 248- 252 Diethylgold sulphate 1 3 1
Alkvlgold(1) complexes 100-102 , wlth acyl hahdes 1 12 C I D h P effrcts 200 Dimrthylaurate(1) 9 8
- , thermal tlc~composrt~on
207
109, .
w ~ t hmetal h a l ~ d e s 114
- -
Cls ~nfluence 216 Dimethylglyoxime complexes
Atomic absorption spectrography "Class b" p r o p e r t l ~ s 22 69, 1 5 7
--, vlbratlonal spectra 220- 221 247 Cluster con?plexes 160- 1 6 4 , Dimethylgold acetate 1 3 0
, wlth aclds 11 1 A t o m ~ cgold 1 0 173-174 Dimc~thylgold(II1)complexes
-, wlth acyl ha11dr.s 1 1 2 , 203 A u r a t ~ o nr e a c t ~ o n s 1 3 5 - 1 37 , hondlng 163-164 , n.m.r. spectra 223---224
, w ~ t halkyl halldrs 2 0 2 2 0 3 A11de romplc~xrs , preparation 160--l h1 , vibrational spectra 221-222
, wlth mc,lcur\ (11) hal1dc.5 - gold(1) 49 , structure, 1 6 1 1 6 2 Dimc,thylgold hydroxide 1 3 0
197-1 9 8 -, n.m.r spectra 2 2 3 Collolds 6 Dimethylsulphoxide complex 8 5
- , wlth metal hallties 1 1 3 - gold(II1) 123, 1 2 8 Covalency In complexes 25 Discriminating power 182-184
Alkyne complexes 148-1 5 1 -, - , electronic spectra 239 C y a n ~ d ecomplexes Diselenocarbamate complexes 8 8
-, Mossbauer spectra 233 A ~ o b e n z e n ecomplexes 79 , gold(1) 45, 256 Disproportionation of gold(1) 22
Alkynylgold c ~ > m p l e x r s103- 104 -
, - , electromc sprctra 239-240 Dithiocarbamate complexes
Alloys of gold 6, 164-1 6 5 -, gold(II1) 76, 1 2 9 , 1 8 5 - gold(1) 54, 6 1
Alluvlal gold 1 Bcnzenethiol reactions 1 9 6 , 201 -, ~nfrarcdspectra 47 - goltl(I1) 5 0
Amhld(,ntate hgands 2 3 Benzimidazoly lgold complexes Cyanide process 4 - , gold(I11) 69, 8 7 , 1 3 1
Am& complrxes 105--106 Cyclooctadrcnr complex 1 4 9 Dithiolate complexes 1 2 , 8 7
, gold(1) 51 Riojogical applications 247-253 Cyclopentad~rnvlgoldcomplexes Dithiooxalate complexes 8 5
- gold(1II) 77-78 2,2 -Bipyridine complexes 102, 106-107 Dithiooxamide complexes 85-86
A m m ~ n emmplexes -, gold(1) 4 9 Cyclopropane r s o m e r ~ s a t ~ o2n 5 6 Dithiophosphate complexes 6 2
-, gold(1) 48 -, gold(In1) 80, 1 3 3 , 1 8 4 , 191-192 Cysterne complexes 251 Dithiophosphinate complexes 62
- gold(II1) 77, 1 3 2 2,2 -Blquinolyl complexes 8 0
-, -, electronlc spectra 239 Bis(dimethy1arsino)benzene Deuterium-hydrogen exchange Electrochemicai analysis 247
-, -, vibrational spectra 213, complexes 8 4 254 Electron affinity 1 4
219 Bis(dipheny1phosphino)methane Dialkylaurates( I) 98-100 Electron configuration 24
Analysis of gold 243--247 complexes 73, 1 5 8 , with acids 1 9 6 Electronic spectroscopy 236-240
Antihistamine properties 252 Bond lengths 261-266 -, with alkyl halides 1 1 8 Electron spin resonance spectra
Aqueous chemistry of gold 1 8 Borohydrides 30 Dialky lgold(II1) complexes 71
Aquo comp!exes 1 2 9 Boron--gold bonds 165-1 6 6 125-1 35 Electrophilic substitution
-, n.m.r. spectra 225 Bromide complexes -, bonding 1 2 5 reactions 194-199
-, vibrational spectra 217 -, gold(1) 6 5 -, thermal decomposition 207 Enzymes 250-251
Arsine complexes -, gold(II1) 9 1
Ferrocenylgold complexes 1 0 6 -, gold(II1) 90 -, stereochemistry 180-181 Penicillamine complex 2 5 3
Fluoride complexes -, Mossbauer spectra 228-234 Linear complexes 1 5 Pentafluorophenylgold complexes
-, gold(II1) 90-91 -, n.q.r. spectra 234 9 9 , 1 2 2 , 135. 1 3 8 . with
--, gold(V) 9 6 - 9 7 -, vibrational spectra 210-21 7 halogens 1 1 5
-, vibrational spectra 2 1 3-214 Halides of gold 31 Maleonitriledithiolate complexes Perchlorate conlplexes, gold(1) 59
Fluorophenylgold complexes Hard and soft acids 22 -, gold(I1) 71 l ,l0-Phenanthroline complexes
-, n.m.r. spectra 226 Hexafluoroaurates(V) 32, 96--97 -, gold(II1) 70, 88-89 -, gold(1) 4 9
Formamidines 1 4 7 Homolytic substitution reactions Manganese-sold bonds 170-1 72, -, gold(II1) 8 0 , 1 3 3 , 1 9 2
Free radical reactions 200-209 200-201 174,176 Phenylgold complexes 107-108,
Hybrid orbitals 1 6 Methyl cyanide complexes 135
G e r m a n ~ u m gold bonds 167-168 Hydrides 30 - , gold(1) 48 -, thermal d e c o m p o s i t ~ o n 1 4 1
Glyoxal p r e p a r a t ~ o n 255-256 Hydridogold(II1) intermediates - , gold(II1) 79
, w ~ t hhalogens 1 15
Gold 196-197 Methylgold(1) complexes 98-100 Phen.{lselenide complex 1 3 1
- , a n t ~ m o n ~ d r10 , Hydrogenation 254 -, photochemistry 11 0
Phenylthioyl rad~cals 200-201
-, n ~ t r ~ d40 e IIydrothermal transfer 2 --,photoelectron spectra 235 Phosphine complexes
, p h o s p h ~ d e 40 , w i t h alkyl halides 1 1 7 -118
Hydroxide complexes, vibrational
--, with alkynes 1 2 0 , gold(1) 5 2
, s e l e n ~ d e 39 spectra 217 , --, bonding 57
-, t e l l u r ~ d e 3, 39 8-Hydroxyquinoline complexes -, with sulphur dioxide 121 , - , p r e p a r a t ~ o n 52, 203-204
Gold(1) 82. 1 3 1 ---,with tetrafluoroethylenr 1 1 9
, -, structure 5 3
- , b r o m ~ d e 31, 36
Methylgold(II1) complc~xes,Imnd , , vibrational spectra 214,
, c h l o r ~ d e31, 33, Immomethy lgold complexes energy 1 4 3
219, 220
-,-, structure 34 105,145 Molecular orhital t h r s r y 2.1
, gold(II1) 8 3 -84, 134
-, c y a n ~ d e 37 I o d ~ d ecomplexes M6ssbaut.r spectra 2 2 6 - ~ 2 3 4
Myocrisin 248
. n.m r spectra 224
- d ~ p h e n y l p h o s p h ~ d5e8 , gold(1) 6 3 Phosphlnc, vhd comolexcs
-, d ~ d 31, e 37 - , gold(II1) 92 - , goltl(1) 99- l 0 0
- , kete,n~dc, 1 0 8 1 0 9 Ionic r a d ~ u s 1 6 , gold(I1) 7 3 , 116, 1 19
, s u l p h ~ d e 38 Ionlsat~onenergles 1 4 -, gold(II1) 1 2 2 , 1 4 3
-, t h ~ o c y a n a t e 37 Ion-selectwe electrodes 247 Photoelectron spectroscopy
Gold(II1) Iron-old bonds 170-173,175 Neutron activation analysis 247 234--235
--, b r o m ~ d e 31, 36 Isocyanate complexes Nitrate complc~xes Phthalocyanine complex gold(I1)
-, c h l o r ~ d e 31, 3 3 -, gold(1) 5 0 -, gold([) 5 9 72
-, -, structure 35 , gold(II1) 1 2 8 , gold(lI1) 8 5 Physical properties of gold 5
-
, , w ~ t halkenes 1 5 0 Isocyan~decomplexes Nobility of gold 18 Piperidinr cornp1t.x 157
, cyanlde 37 , bondlng 45 Nuclear magnetic resonance Porphyrin complex 8 2
-, f l u o r ~ d e31, 32 -, gold(1) 45, 1 1 0 , 144, 1 4 6 , 1 5 7 spc~ctroscopy 223-2 2 6 Potable gold 6
-, fluorosulphate 39 -, gold(II1) 7 6 Nuclear quadrupolc resonance Pourbaix diagram 1 9
- h y d r o x ~ d e 38 Isomerlsation o f hydrocarbons spectroscopy 234 Pseudohalides 37
-, n ~ t r a t e 40 254-255 Purification of gold 5
-, o x ~ d ec h l o r ~ d e38 Isomer s h ~ f t s227-231 Purple of Cassius 7
-, s e l e n ~ d e38 Isotopes of gold 7 Occurrence of gold 1 Pyrazolylgold(1) 51
-, s u l p h ~ d e38 Olefin metathesis 256 Pyridine complexes
Gold(V) Ligand field theory 1 7 Orlho-metallation reactions 1 3 6 , gold(1) 48
-, f l u o r ~ d e 31, 32, 9 6 Ligand substitution reactions Oxidation o f gold(1) 201-203 -, gold(II1) 7 9 , 132, 183-186
Gold coatmg 256-257 -, mechanism for gold(1) Oxidation-reduction potentials , vibrational spectra 219
Gold-gold bonds 157-160 191-194 18 2-Pyridylgold(1) 104, 1 1 0
G r a v ~ m e t r ~analysls
c 244-245 -, mechanism f o r gold(II1) Oxidation states 1 0
179-193 Oxidative addition 1 1 2 , 1 1 6 , 1 1 7 , Quadrupole splittings 231-233
Halide complexes -, role of entering ligand 1 3 7 . ~ 1 3 81, 4 7 , 201-203
-, electronic spectra 236-240 182-185 Oxonium salts 5 8 Radio-isotopes 2 5 3
-, electronic structure 24, -, role of leaving ligand 185-186 Oxygen--donor complexes, Sadiotherapy 2 5 3
236--239 -, solvent effects 1 8 8 gold(1) 5 8 Reactivity o f gold 9
Recovery of gold 4 T h ~ o m a l a t ecomplexes 248-253
Reduction of gold(II1) complexes Th~omorphoim-3-onecomplexes
203-207 204
Reductive elimination 1 1 7 , Thlosulphate complexes, gold(1)
141-143, 1 9 5 , 205-207 58, 1 5 7 , 2 0 5 , 2 4 8
Reef gold 2 Thmurea complexes 2 4 4
Tln--gold bonds 1 6 7 , 1 6 9
Sanocrysln 248 T ~ ~ r ~ m ea nt ra l~bcs ~ s2 1 5
Selenocyanate complexes, gold(1II) T o x l c ~ t y 252-253
128 I'rcn\ effect 26, !88-1 8 9
Sillconrgold bonds 167 fran\ rnflui.nce 26, 214-222, 223
S-methlonlne complex 204 T r a n & h o nmetal-gold bonds
Solgnnol 248 169-176
Solvent extractwn ol gold bonding 176
2 4 8 , 246, 2 17 yrrpdratlon 170- 1 7 4
S p e c t r o p h o t o m r t r ~ canallsls , propr,rt~e\ 1 7 4 - 1 7 5
2i.5 2 16 , structurv 1 7 5 I 7 6
S t a b ~ l i t yof complcxc.~ 22 , v ~ b r a t ~ o nspectra
al 21 1
Stereochem~stry I'rialkylgold(I1I) complexes 1 2 3
- , gold(1) complrxcs l O , rromerisat~on1 3 8 - 1 3 9
- , gold(I1) complc~xes I l , thermal decomposltlon
-, gold(II1) complexcbs 1 2 , 1 X2 205 207
-, gold(V) complcxrs 1 3 , vibr,~tionalspectra 2 2 1
Sterlc ellects 186 - I 8H -, w:th aclds 1 1 0 , 195- 1 9 6
S t ~ h ~ complcxc~s
nr , wgth ha1ogc.n~ 140
, gold(l) 5 2 , w ~ t hmercuryiII) halides lcf7
-, gold(II1) 8 4 , w ~ t hn1trogc.n oxldes 14 1
Succ~nlmidecomplcxcs, goltl(ll1) , wlth sulphur d l o x ~ d e1 4 0
78 Tr~fluoromethylgoldcomplexc~s
Sulphate complexes, golti(1) 5 9 201, 2 0 3
Sulphinate complexcs 1 2 1, 140 Trlmethylsiloxy complex 1 3 0
Sulphite, complexcs 8 5 Trlpvrdzolylborate complextx\
81,190
Tctracyano~.thylt.nccomplt~xcs
119, 151
Vihrational spectroscopy
Tetrahydroalum~nate 30
T r t r a m c t h y l d u r a t ~ 1 2 1 122 210-223
Tetramethy l e t h y l c n t d ~ a r n ~ n r Vinyl acetate manufacture 255
complex 1 9 1 Vinylgold complexes 1 0 7 . 1 5 1
, thermal decomposition 1 4 2
Trtrazolatt, complexes 122
T h ~ o c y a n a t ec o m p l e x t q golti(II1) -, with acids 111
128, 181 1 8 2 -, with mercury(I1) bromide 113
Thioglucosc~c o m p l r x ~ s248 253 Vitamin Blz 9 8
Thiolate complexes
-, gold(1) 61, 62, 64, 248-252 Xanthate complex 1 3 1
-, gold(II1) 1 3 2 X-ray structures 261-266