Synthesis and properties of some p-diketimines derived from

acetylacetone, and their metal complexes

S. G. MCGEACHIN
Departtr~entof Cl~ernistry,Ur~iversityof Alberta, Edmor~torl,Alberta
Received February 13, 1968

The synthesis of a number of diketimine ligands of structure 1 is reported. These give bis-bidentate
chelates of type 2 with Cu(II), Ni(II), and Co(I1). Optical spectra, magnetic moments and, in a number
of instances, solution molecular weights are recorded for these complexes. On the basis of these, it is
concluded that the complexes unsubstituted on nitrogen, adopt a square planar stereochemistry in
contrast to the others which are all pseudotetrahedral.
Canadian Journal of Chemistry, 46, 1903 (1968)

Introduction this type by a mild method of general applic-

While complexes of P-diketones have enjoyed
study for close to one hundred years those of
simple analogues in which one or both oxygen
atoms are replaced by other elements have only
recently received much attention. Worthy of
note is the examination of complexes of P-
amino-C$-unsaturated ketones (I), monothio-P-
diketones (2), and dithioacetylacetone (3).
Insofar as we are aware, no particular attention
has been paid to those of P-diketimines, in
which both oxygen atoms are replaced by
nitrogen, although isolated examples of such
complexes do exist (4). This in part may be due
to the rarity of the required ligands ( 5 ) , and to
their considerable hydrolytic instability. We
herein report the synthesis of several ligands of
TABLE I
Characterization of the ligand fluoborate salts
ability and record the preparation and properties
of their copper, nickel, and cobalt complexes.
Results
The ligands 1 (R = H, Me, Et, i-Pr, Ph), which
are vinylogous amidinium salts, were synthesized
by Reaction Scheme 1 from the readily available
corresponding enamino ketones (6). A few
examples of this method for the synthesis of such
salts have been previously reported (7). It de-
pends on the propensity of triethoxonium fluo-
borate for 0-alkylation of the enamino ketone,
which renders the carbon of the original carbonyl
function readily susceptible to nucleophilic at-
tack in the resulting vinylogous imino ether.
Some characteristics of the ligand fluoborate

Compound analysis Ultraviolet spectrum Nuclear magnetic resonance

R %C %H %N Melting point ("C) k,,, M~OH(E) (CD3COCD3)r
H Calcd.
Found
Me Calcd.
Found
Et Calcd.
Found
i-Pr Calcd.
Found
Ph Calcd.
Found

*Singlet.
tDoublet.
rMultiplet.
$Broad, unresolved band.
JJTriplct.
1904 CANADIAN JOURNAL O F CHEMISTRY. VOL. 46, 1968

TABLE I1
Characterization of the free bases from the ligand fluoborate salts 1
- -

Compound analysis Nuclear magnetic resonance

R %c %H %N Melting point (OC) (CDC1,)r
Calcd. - - -
Found - - -
Calcd. 66.62 11.18 22.20
Found 66.66 11.07 22.03
Calcd. 70.06 11.76 18.16
Found 70.06 11.65 18.39
Calcd. 81.56 7.25 11.19
Found 81.63 7.41 11.05
'Singlet.
tDoublet.
SMultiplet.
§Broad, unresolved band.
Triplet.
'[Quartet.
**A satisfactory analysis was not obtained, but Mol. Wt. Calcd. for C5HloN,: 98.0844. Found (mass spectrometry): 98.0844.

+ + -+ CH3'-.p(cH3
CH371/CH3 Et30BF4- RNH2 CH3\l;yCH3
RNH 0 R F H OEt RNH HNR

* wCH3
+
RNH HNR
+
( E L I N ) ~ M X4-~ IIOCH~-/CH~OH

- - CH3 R

salts are given in Table I. They are all stable
crystalline substances but are best protected
from moisture. The corresponding free bases
could be obtained by deprotonation of these
salts by methoxide ion in anhydrous methanol.
Data concerning these are recorded in Table 11.
We chose for study the bis-bidentate copper,
nickel, and cobalt complexes of these ligands, as
most studies on related species have involved
these metals. They were prepared, as shown in
Reaction Scheme 2, essentially by the non-
aqueous procedure of Everett and Holm (8) but
with the use of methanol (in which all of the
reactants are freely soluble) in place of t-butanol
as solvent. Analytical and other data are given in
Table 111. In the preparation of the nickel and
copper complexes 2 (R = H) the isolated prod-
ucts from the above reaction were not the
simple bis-bidentate chelates but rather corn-
plexes of these with tetraethylammonium halide
of the stoicheiometry Et4NX(ML2),. These were
decomposed by shaking with water at room
temperature to give the simple chelates. By heat-
ing them at 220 "/0.01 mm the simple chelates
could again be obtained in the form of subli-
mates. It is likely that the initial product ob-
tained in the preparation of the Co(I1) complex
in this series is also of this type as it is benzene
insoluble. It proved to be too unstable toward
air to permit purification and analysis. The
nature of these complexes is not known. The
ligand field spectra of the solids and their solu-
tions in methanol were the same as those of the
simple chelates themselves. The nuclear mag-
netic resonance (n.m.r.) spectrum of the dia-
magnetic nickel complex in deuterated dimethyl
 TABLE I11
Characterization of the metal complexes 2

%C %H %N
R Metal Melting point ("C) Color Calcd. Found Calcd. Found Calcd. Found
green
-- red
4
H Cot - orange
Me u 150* purple
Me Ni 165-166 brown
Me Co 164-165* orange
Et Cu 98-101 blue-black
EF-
-~
Ni 65-66 brown
Et Co 50-5 1 orange
c
11 164 green-black
Ph Ni 167-168 dark green
Ph Co 143-145 orange-red
*Decomposed at the melting point.
?This compound was too unstable t o permit analysis, but Mol. Wt. Cali:d. for C,oH,sN4Co: 253.0864,Found (mass spectrometry): 253.0867.

sulfoxide between 30-100 " was a superirn-
position of the spectra of the simple chelate and
tetraethylammonium halide in the same solvent.
None of the N-substituted ligands gave similar
complexes.
No chelates of the series with R = i-Pr
could be obtained by the above method or by
the similar but more vigorous conditions utilized
by Collman and Kittleman in the synthesis of
tris(P-ketoamino)Cr(III) complexes (9). We
conclude that these are probably too sterically
hindered to exist in either tetrahedral or planar
forms, a fact also suggested by an examination of
molecular models. For the complexes listed in
Table I11 optical spectra between 5000 and
25 000 cm-I were measured. These were all
virtually identical in both the solid state and in
non-coordinating solvents. They are recorded in
Table IV and graphically in Figs. 1-3. Effective
magnetic moments were also obtained as shown
in Table V. In addition the solution molecular
weights of those complexes of sufficient stability
were measured osmometrically and are given in
Table VI. A discussion of the data obtained is
given below separately for each metal series.
Copper Complexes
The complex with R = H is monomeric in
solution. Its ligand field spectrum possesses only
one band centered at 15 600 cm-l. This single
band is very similar to that observed in known
square planar bis(salicy1ideniminato)copper com-
plexes at around 16 000 cm- (10-13). We ac-
cordingly assign this coordination geometry to
the complex. The value of peff of 1.86 BM is
consistent with the slightly lower orbital contri-
bution expected for this stereochemistry (14),
and is to be compared with those of the three
N-substituted complexes which lie between 1.94
and 1.98 BM. Of these three substituted com-
plexes only one, 2 (R = Me), gave an acceptable
value for the molecular weight as a monomer in
solution, the remaining two giving values more
than 5 % below that calculated for the mono-
meric species. The close resemblance in their
electronic spectra, however, strongly suggests
that they are all similarly constituted. These
spectra are very different from that of the un-
substituted case, and exhibit evidence of three or
four bands. In this they bear a resemblance to
the spectrum of bis(N-t-butylsalicy1ideniminato)-
Cu(I1) (13) which has been sllown by x-ray
analysis to possess a distorted tetrahedral geom-
etry (15). Splitting of the ground and excited
states with a resultant multiplicity in the one
transition allowed for perfectly tetrahedral cop-
per has been predicted for the distorted tetra-
hedral orientation (16). The dangers in assigning
extreme square planar or tetrahedral geometries
to four-coordinate copper from ligand field
spectra have been pointed out (17). We conclude
that while the three N-substituted complexes are
almost certainly of the distorted tetrahedral type
there is no evidence to indicate how close to pure
tetrahedral they may be individually.
Nickel Complexes
The complex with R = H is diamagnetic in
both the solid state and in solution. Its n.m.r.
spectrum has absorptions for the methyl and
 CANADIAN J O U R N A L OF CHEMISTRY. VOL. 46. 1968

5 9 13 17 21 25
WAVELENGT H ( crn-1 x lo6)
FIG. 1. Optical spectra of the bis-bidentate copper complexes.
McGEACHIN: SYNTHESIS A N D PROPERTIES O F p-DIKETIMINES

FIG.2. Optical spectra of the bis-bidentate nickel complexes.

 CANADIAN JOURNAL O F CHEMISTRY. VOL. 46, 1968

WAVELENGTH ( cm-lx 10'~)

FIG.3. Optical spectra of the bis-bidentate cobalt con~plexes.
 McGEACHIN: SYNTHESIS AND PROPERTIES O F p-DIKETIMINES 1909

TABLE IV
Spectral data for con~plexes2 between 5000 and 25 000 cm-'
.-

Metal Medium Spectral maxima and extinction coefficients

Soln. 15 600 (53)
Solid 16 100 (max)
Soln. 7400 (66) 12 500 (sh) 19 300 (1850) 23 200 (sh)
Solid 7400 (max) 12 000 (sh) 19 300 (max) 22 500 (sh)
Soln. 6060 (51) 12 500 (sh) 17 800 (1620) 22 600 (411)
Solid 6450 (max) 12 000 (sh) 16 700 (max)
Soln. 5900 (41) - 14 800 (1 107) 20 400 (shj
Solid 5900 (max) 11 300 (sh) 15 000 (max) 19 600 (sh)
Soh. 18700 (115)
Solid 18 700 (max)
Soln. 9100 (sh) 9500 (28) 10 750 (sh) 17 100 (sh) 22 750 (sh) 24 400 (1900)
Solid 9100 (sh) 9 500 (max) 10 200 (sh) 17 250 (sh) 22 200 (max) -
Soh. 7400-9100 (28) 10 250 (sh) 17 200 (123) 22 200 (sh) 23 700 (2380)
Solid 10 200 (n~ax) 10 500 (sh) 17 200 (max) - -
Soln. 7350 (46) lOOOO(sh) 16000(310) - 23 600 (sh)
Solid 7400 (sh) 8 350 (n~ax) 11 100 (sh) 15 900 (max) 19 500 (sh) -
H Co Soln. 5500-6500 (7) 10 750 (20) 20 400 (sh) 22 200 (sh) 24 100( sh)
Solid - - 10 500
.. fn~axl
,-----
- - ~, - - -
Me Co Soln. 9100 (59) 10 000 (sh) - 13 300 (sh) 21 000 (sh) 22 500 (880)
Solid 9000 (max) 10 200 (sh) 10 600 (sh) 13 300 (sh) 21 000 (sh) 22 500 (max)
Et Co Soln. 9700 (67) 11 800 (sh) - - 21 000 (sh) 22 500 (1600)
Solid 9700 (maxj 10 200 (shj 13 100 (sh) . .
14700 (sh) - -
ph co S o ~ n . 9400 (135j 11 loo (shj 12900 (shj - 21 800 (sh) -
Solid 9350 (max) 11 800 (sh) 12800 (sh) - 21 500 (sh) -

TABLE V TABLE VI
Magnetic moments of the complexes 2 Molecular weights in solution of the con~plexes2

Solid Solution Molecular weights

R Metal P,rr BM Solvent Pcrr BM R Metal Solvent Calcd. Found

H Cu PhH 257 250
Me Cu PhH 313 323
- -~

~ t - ~i ~e;cd 365 351

Ph Ni Me,CO 557 555
H Ni d ia dia Et Co PhH 365 344
Me Ni 3.13 CHzC12 3.08 Ph Co Me2C0 557 547
Et Ni 3.12 CHCIs* 3.11
Ph Ni 3.21 CHZCIz 3.12
anato)lVi(II) (18), and can be assigned to a
singlet-singlet transition centered on nickel.
This complex is therefore similar to other four-
*Freed from ethanol. coordinate nickel complexes, with oxygen, sulfur,
or nitrogen donor atoms, in preferring to adopt
vinylic protons at T 8.14 and 5.40 (triplet, a planar diamagnetic configuration in the ab-
J = 2 c.p.s.), which correspond within 5 c.p.s. sence of significant steric strain. For each of the
to their positions in the free ligand base. The three N-substituted complexes the values of p,,,
protons on nitrogen appear as a broad band, for the solid and solution are within 2 % of each
T 6.1-6.6, and are responsible through long other. These values which range from 3.08 to
range coupling for the splitting of the vinylic 3.22 BM lie slightly lower than those, 3.18 to
proton to a triplet. The ligand field spectrum of 3.37 BM, observed for fully paramagnetic bis-
the c o m ~ l e xexhibits one band at 18 700 cm-I (P-ketoamino)Ni(II) complexes of proven pseu-
which is identical in position with that of known dotetrahedral geometry. Since, however, molec-
square planar diamagnetic bis(dipivaloy1meth- ular weight studies on the three, indicated
1910 CANADIAN JOURNAL OF CHEMISTRY. VOL. 46, 1968

absence of association in solution at molarities Co(I1) (4) (21), which have been assigned a
of the same order of magnitude as those used in square planar configuration. In these latter it is
the determination of perf, one may conclude considered characteristic of low spin planar
that they are likewise strictly four-coordinate Co(I1). We therefore assign this geometry to the
and adopt a pseudotetrahedral geometry in both complex in question. Holm and Everett have
the solid and in non-coordinating solvents. This
u shown for the similarly constituted complex 5
is supported by the ligand field spectra, which are that an equilibrium between low spin planar and
virtually identical in solid and solution phases high spin tetrahedral forms exists in solution, in
and show features similar to those of the above- which the latter is present to about 70 % at room
mentioned pseudotetrahedral bis(e-ketoamino)- temperature. The evidence presented here does
complexes (8). The evidence does not permit us not exclude 5 % or less of the tetrahedral form in
to exclude 5 % or less of the diamagnetic planar equilibrium with the planar in solution. The
form in equilibrium in solution with the tetra- absence, however, of any significant concentra-
hedral, but it is apparent that the latter must tion of the tetrahedral form in solution indicates
greatly predominate. This is to be compared that for this ligand there is a greater Free energy
with similarly substituted bis(aminotroponeimi- difference between the two forms than exists
nato)Ni(II) complexes 3 which at room tempera- between those of 5. This difference can scarcely
ture are < 1 % paramagnetic for R = CH,, be steric in origin and is probably a consequence
50-75 % for R = Ar, and > 99 % for R = Et of the greater field strength of the diketimine
(19). It is evident that the greater steric repulsions
ligand.
among the substituents on nitrogen expected for The remaining three complexes have perfbe-
the six membered chelate rings of 2 destabilize tween 4.28 and 4.51 BM and are therefore fully
the planar form relative to the tetrahedral much high spin. The adequate stability of two of them
more than in the five membered rings of 3. toward oxygen permitted molecular weight
determinations to indicate their monomeric na-
ture in solution. The near identity of the optical
spectra of the complex with R = Et and that
with R = Me in solution makes it clear that the
latter must also be monomeric under these
conditions. In general the ligand field spectra of
the three are very similar and feature a broad
band at -10 000 cm-I with a high frequency
shoulder at -12 000 - 13 000 cm-', and a vis-
ible band at -22 000 cm-I with a low frequency
shoulder. These spectra, although shifted to
higher frequencies, closely resemble in outline
those of bis(N - isopropylamino - 3 - penten - 2 -
Cobalt Complexes onato)Co(II) (21) which has been convincingly
A situation exists with these complexes similar shown to possess a pseudotetrahedral structure.
to that for the other two seiies. The complex We therefore consider that the three N-substi-
with R = H is low spin in both the solid and tuted complexes have this structure.
benzene solution. The two values of perf are The cobalt complexes show an increasing
within 4 % of each other and in the range, 2.2 to lability toward oxygen with decreasing size of
2.9 BM, considered characteristic of low spin the substituent on nitrogen. In the case of the
Co(I1) (20). Its ligand field spectrum, identical in ligand with R = H it proved possible to syn-
the solid and in solution, is characterized by the thesize the tris(diketimine)Co(III) complex by
presence of a narrow band at 11 000 cmP1 passing dry air into a solution of the ligand and
( E 20). This band, although shifted to higher Co (11) in the ratio of 3 :1. This is a deep red
frequency, closely resembles in shape and in- diamagnetic complex which has no discrete band
tensity that observed in the spectra of other low in the visible or near infrared portions of the
spin four-coordinate complexes of cobalt, such spectrum. Although oxidation clearly took place,
as N,N'-ethylenebis(4-amino-3-penten-2-onato)- attempts to synthesize the corresponding tris-
 McGEACHIN: SYNTHESIS AND PROPERTIES OF (J-DIKETIMINES 1911
Co(II1) complexes of the substituted ligands The ligand salts may all be further purified by recrystal-
under the above conditions yielded none of the lization from acetone - ethyl acetate. The corresponding
free bases were obtained from the salts by treatment with
desired compounds. an equivalent amount of 0.5 M sodium methoxide in
methanol. The methanol was removed it1 oacuo, at, or
Experimental below room temperature, and the residue extracted into
General benzene. The benzene solution was filtered and taken
Melting points were taken On a Kofler point cautiously to dryness in vacua at room temperature, In
apparatus and are uncorrected. were performed the phenyl substituted case the product was crystallized
by the Microanalytical Laboratory of this department. from pentane at 0 0 ~ The . others were sublimed at
All measurements on the complexes were performed on 50-100 010.1 mnl on to a cold finger (< 0 o C ) , Character-
freshly purified samples. Optical spectra were obtained izing data are given in ~ ~II. b l ~
on a Car); 14 spectrophotometer. Solution spectra were
taken in benzene or chloroform (ethanol free). Solid Bis-bidetztrrte Con~plexes2
state spectra were measured by absorption (pressed KBr These were all generated in the same way by the
disk) between 5000and 10 000 cnl-I, and by reflectance addition under nitrogen of ca. 1 mmole of Et4NMX4
between 10000 and 25 000cn1-I. Magnetic suscepti- (M = CU, Ni, CO; X4 = C1, or Br,) in anhydrous
bilities of solids were obtained by the Faraday technique methanol (5-10 ml) to a stirred solution of 2 eq~~ivalents
with X, for HgCo(CNS), = 16.44 (k0.08) x 10-6 c.g.s. of the ligand fluoborate salt in 4 equivalents of anhydrous
at 293 "K taken as the reference (22). Magnetic suscepti- 0.5 N sodium methoxide in methanol. The reaction
bilities of substances in solution were obtained by a mixture was then stirred for a further IOmin. The
nuclear magnetic resonance (n.m.r.) method (23). The reaction was kept at room temperature throughout and
solutions for this were prepared under nitrogen, placed the product was isolated as follows:
in n.m.r. tubes, transferred to a high vacuum line, 2 (R = H; M = Ni, Cu)
degassed, and sealed. The Curie Law was used in the The precipitate formed was collected and shaken with
evaluation of peer from X M corrected. Molecular weights water and benzene until complete dissolution had oc-
in solution were determined on a Mechrolab Osmometer. curred. The product was isolated from the benzene layer
Accurate molecular weights were obtained on an A.E.I. and recrystallized from benzene-hexane.
M.S.9 double focussing mass spectrometer. 2, (R = H; M = Co)
Preparation of theLigands 1, (R = H, Me, El, i-pr, pI1) The precipitate formed was removed by filtration a n d
~h~ preparations of the five ligand salts are very dried under nitrogen. It was then transferred rapidly to a
similar and only two are given in detail. Characterizing sublimation apparatus and the complex isolated by
data are given in Table I. sublinlation at 180-220 "C/0.005 mm. It was then sealed
inin~ediatelyin a vial under nitrogen.
Fluoborate 1, (R = H )
4-An1i110-3-penten-2-im1?i01ziu1n
Triethoxonium fluoborate (24) (25 g, 0,131 mole) dis- 2' (R = M = C1[, Ni, Co; and = Me; = Ni)
solved in dichloromethane (50 ml) was added to a stirred The precipitate formed was collected and dissolved in
solution of 4-amino-3-penten-2-one (13 g, 0.131 mole) in benzene. The solution was then filtered. Crystallization
the same solvent ml). ~h~ resulting solution was was induced by the addition of methanol to the con-
allowed to stand for 30 min. A solution of anhydrous centrated solution.
3.28 N ethanolic ammonia (40 ml) was then added 2, (R = Me; M = C& Co)
dropwise over a period of 20 min to the stirred reaction The precipitate formed was collected and dissolved in
mixture. This was allowed to stand a further 10 min, and warm hexane. The solution was filtered, concentrated,
was then filtered to remove the a m n ~ o n i u nfluoborate
~ and d ~ w e to d crystallize to give the product.
(3 g). The filtrate, upon concentration at room tempera- 2, (R = Et; M = Cu, Ni, Co)
ture in vacrro to ca. 113 of its volume, deposited the The reaction mixture was taken t o dryness in oacuo
crystalline immonium salt (11 g, 45%) in pure form. and the residue washed with warm benzene. The benzene
The three N,N'-dialkyl analogues were prepared by solution was filtered, concentrated, and crystallization
this procedure. In all cases a small amount of anline induced by the addition of methanol with strong cooling.
fluoborate salt had to be removed prior to concentration The con~plexeswere purified by sublimation at 100-
of the reaction mixture. Yields ranged from 40 t o 60%. 150 "C/0.01 mnl except for the phenyl series which were
- 3 - p e t l ~ e ~ - 2 - i l l l ~ ~ l ~ ~ ~ ~ ~ l ~ These
N , ~ ' - ~ ~ p ~ e n y ~ - 4 - a l l l ~ l l oFllloborate
are all sensitive t o atmospheric moisture and the cobalt
1, (R = Ph)
Trietlloxonium fluoborate (4 g, 0.021 mole) in di- series t o oxygen. Therefore, they were stored in sealed
chloromethane was added dropwise to a stirred vials under nitrogen. Yields ranged from 30 to 80%.
solution of 4-%-ph~nylamino-3-penten-2-one (3.68 g, Tris(4-arnir10-3-per1tet1-2-01zei1ninafo) Co (111)
0.021 mole) in the same solvent (10 ml). The mixture was A solution of Et4NCoBr4 (327 mg) in methanol
allowed to stand for 30 min and a solution of aniline (5 ml) was added under nitrogen to a stirred solution of
(1.96 g, 0.021 mole) in dichloromethane (5 ml) was 4-amino-3-penten-2-immoniunl fluoborate (285 mg) in
added. After I h the solvent was removed completely in 6.1 ml of 0.5 N sodium methoxide in methanol. An im-
vacuo and the residual oil was dissolved in hot ethyl mediate yellow precipitate of the [L,Co(II)],Et,NBr
acetate and allowed t o crystallize to give the product complex (see text) formed. Stirring was continued and
(5.91 g, 83 %). dry air was passed into the apparatus for 30 min. The
1912 CANADIAN JOURNAL OF CHEMISTRY. VOL. 46, 1968

solution darkened and a red precipitate formed. This L. C. DORMAN.Tetrahedron Letters, 459 (1966).
was collected and crystallized from benzene. The ana- N. H. CROMWELL.Chem. Rev. 38,83 (1946).
lytical sample had m.p. 215-220 "C (decamp.). It did not H. MEEWEIN, W. FLORIAN, N. SCHON,and G . STOPP.
give a satisfactory con~bustionanalysis. Ann. 641, 1 (1961); H. BREDERECK, F. EFFENBERG,
Mol. Wt. Calcd. for C,,H2,N6Co: 350.1629. Found and D. ZEYFANG.Angew. Chem. Intern. Ed. Engl.
4,242 (1965).
mass spectrometry): 350.1630. G . W. EVERETT, JR.and R. H. HOLM. J. Am. Chem.
SOC.87,2117 (1965).
Acknowledgments J. P. COLLMAN and E. T. KITTLEMAN.Inorg. Chen~.
1,499 (1962).
The author is grateful to Mr. G. Harvie for E. C. LINGAFELTER, G . L. SIMMONS,B. MOROSIN,
C. SCHERINGER, and C. FREIBURG.Acta Cryst. 14,
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