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26
Cobalt, Rhodium and Iridium

26.1 Introduction unexpectedly to yield the anticipated metal b u t

a l s o p r o d u c e d h i g h l y t o x i c f u m e s (AS4O6).
Although hardly a n y metallic cobalt w a s used In 1803 b o t h r h o d i u m a n d i r i d i u m w e r e d i s -
until t h e t w e n t i e t h c e n t u r y , its o r e s h a v e b e e n c o v e r e d , like their p r e c e d i n g n e i g h b o u r s i n t h e
( 1 )

used for thousands of years t o impart a blue p e r i o d i c table, r u t h e n i u m a n d o s m i u m , in t h e b l a c k

c o l o u r t o g l a s s a n d p o t t e r y . I t is p r e s e n t in r e s i d u e left after c r u d e p l a t i n u m h a d b e e n d i s -
Egyptian pottery dated at around 2600 B C a n d s o l v e d in a q u a r e g i a . W . H . W o l l a s t o n d i s c o v e r e d
Iranian glass b e a d s o f 2 2 5 0 B C . Ï T h e source r h o d i u m , n a m i n g it after t h e G r e e k w o r d ρόδον
of t h e b l u e c o l o u r w a s r e c o g n i z e d in 1735 b y for " r o s e " b e c a u s e o f t h e r o s e - c o l o u r c o m m o n l y
t h e S w e d i s h c h e m i s t G . B r a n d t , w h o isolated a f o u n d i n a q u e o u s s o l u t i o n s o f its salts. S . T e n n a n t
very impure metal, or "regulus", which h e n a m e d discovered iridium along with osmium, and named
"cobalt r e x " . In 1780 T. O . Bergman showed it after t h e G r e e k g o d d e s s Iris ( i p t η, ί ρ ι δ - ) , w h o s e
this t o b e a n e w e l e m e n t . I t s n a m e h a s s o m e sign w a s t h e r a i n b o w , b e c a u s e o f t h e variety of
resemblance t o the G r e e k w o r d for " m i n e " but is c o l o u r s o f its c o m p o u n d s .
a l m o s t certainly d e r i v e d f r o m t h e G e r m a n w o r d
Kobold f o r " g o b l i n " o r " e v i l spirit". T h e m i n e r s
of northern European countries thought that 26.2 The Elements
t h e spitefulness o f s u c h spirits w a s r e s p o n s i b l e
for o r e s w h i c h , o n s m e l t i n g , n o t o n l y failed 26.2.1 Terrestrial abundance and
distribution
^ "Smalt", produced b y fusing potash, silica and cobalt
R h o d i u m a n d iridium a r e exceedingly rare
oxide, can be used for colouring glass or for glazing
pottery. T h e s e c r e t o f m a k i n g this brilliant b l u e p i g m e n t w a s elements, comprising only 0.0001 and 0.001 p p m
a p p a r e n t l y lost, t o b e r e d i s c o v e r e d i n t h e fifteenth century. of t h e e a r t h ' s crust r e s p e c t i v e l y , a n d e v e n
L e o n a r d o d a V i n c i w a s o n e o f the first t o u s e p o w d e r e d s m a l t
as a " n e w " p i g m e n t w h e n painting his f a m o u s "The M a d o n n a
o f the Rocks". 1 L . B . H U N T , Platinum Metals Rev. 31, 3 2 - 4 1 (1987).

1113
1114 Cobalt, Rhodium
cobalt ( 2 9 p p m , i.e. 0 . 0 0 2 9 % ) , t h o u g h w i d e l y
distributed, s t a n d s o n l y thirtieth in o r d e r of
a b u n d a n c e a n d is less c o m m o n t h a n all o t h e r
e l e m e n t s of t h e first transition series e x c e p t
s c a n d i u m (25 p p m ) .
M o r e than 2 0 0 o r e s a r e k n o w n t o c o n t a i n
cobalt b u t o n l y a f e w a r e of c o m m e r c i a l v a l u e .
T h e m o r e i m p o r t a n t a r e a r s e n i d e s a n d sulfides
such as smaltite, C0AS2, cobaltite (or c o b a l t
g l a n c e ) , C o A s S , a n d linnaeite, C03S4. T h e s e
are i n v a r i a b l y a s s o c i a t e d w i t h n i c k e l , a n d often
also with c o p p e r a n d lead, a n d it is usually
o b t a i n e d a s a b y p r o d u c t o r c o p r o d u c t in t h e
recovery of these metals. T h e world's major
s o u r c e s of c o b a l t a r e t h e African c o n t i n e n t a n d
C a n a d a with s m a l l e r r e s e r v e s in A u s t r a l i a a n d
the f o r m e r U S S R . A l l t h e p l a t i n u m m e t a l s a r e
generally a s s o c i a t e d w i t h e a c h o t h e r a n d r h o d i u m
and iridium therefore o c c u r w h e r e v e r t h e o t h e r
p l a t i n u m m e t a l s a r e found. H o w e v e r , t h e relative
p r o p o r t i o n s of t h e i n d i v i d u a l m e t a l s a r e b y n o
means constant and the more important sources
of r h o d i u m a r e t h e n i c k e l - c o p p e r - s u l f i d e o r e s
found in S o u t h Africa a n d in S u d b u r y , C a n a d a ,
w h i c h c o n t a i n a b o u t 0 . 1 % R h . I r i d i u m is usually
o b t a i n e d from n a t i v e o s m i r i d i u m (Ir ~ 5 0 % ) o r
i r i d i o s m i u m (Ir ~ 7 0 % ) f o u n d chiefly in A l a s k a
as w e l l a s S o u t h Africa.
26.2.2 Preparation and uses of the
{2)
elements
( 2 , 3 )
T h e p r o d u c t i o n of c o b a l t is usually s u b s i d i a r y
to that of c o p p e r o r nickel a n d t h e m e t h o d s
e m p l o y e d differ w i d e l y , d e p e n d i n g o n w h i c h of
t h e s e it is a s s o c i a t e d with. In g e n e r a l t h e o r e
is subjected t o a p p r o p r i a t e r o a s t i n g t r e a t m e n t
so as t o r e m o v e g a n g u e m a t e r i a l a s a slag
a n d p r o d u c e a " s p e i s s " of m i x e d m e t a l a n d
o x i d e s . In t h e c a s e of arsenical o r e s , AS2O6 is
condensed and provides a valuable byproduct.
In t h e c a s e of c o p p e r o r e s , t h e p r i m a r y p r o c e s s
2
J . H I L L , C h a p . 2 i n D . T H O M P S O N ( e d . ) , Insights into
ciality Inorganic Chemicals, pp. 5 - 3 4 , R . S . C . , Cambridge,
1995.
3
Kirk-Othmer Encyclopedia of Chemical Technology,
e d n . , V o l . 6 , p p . 7 6 0 - 7 7 , I n t e r s c i e n c e N e w York, 1 9 9 3 .
and Iridium Ch. 26
l e a v e s a spent electrolyte from w h i c h iron is
precipitated as the hydroxide by lime and the
c o b a l t t h e n s e p a r a t e d b y further electrolysis.
N i c k e l ores y i e l d acidic sulfate o r c h l o r i d e
s o l u t i o n s a n d t h e m e t h o d s u s e d to s e p a r a t e t h e
n i c k e l a n d c o b a l t i n c l u d e : (a) precipitation of
c o b a l t a s t h e sulfide; (b) o x i d a t i o n of c o b a l t a n d
p r e c i p i t a t i o n of C o ( O H ) ; (c) m a k i n g t h e solution
3
a l k a l i n e with NH3 a n d r e m o v a l of n i c k e l either
as t h e s p a r i n g l y s o l u b l e ( N H ^ N K S O ^ . o ^ O
or b y selective r e d u c t i o n t o t h e metal b y H 2
u n d e r p r e s s u r e ; (d) a n i o n e x c h a n g e , utilizing t h e
preferential f o r m a t i o n of [ C o C L * ] . 2 -
W o r l d p r o d u c t i o n of c o b a l t in 1 9 9 5 w a s a b o u t
2 0 0 0 0 tonnes, considerably below capacity. T h e
major producing countries are Zaire, Zambia,
C a n a d a , F i n l a n d a n d t h e f o r m e r Soviet U n i o n .
T h e largest u s e of cobalt is in t h e p r o d u c t i o n
of c h e m i c a l s for t h e c e r a m i c a n d paint industries.
In c e r a m i c s t h e m a i n u s e n o w is n o t t o p r o v i d e
a blue colour, but rather white by counterbalanc­
ing t h e y e l l o w tint arising from iron i m p u r i t i e s .
B l u e p i g m e n t s a r e , h o w e v e r , u s e d in paints a n d
inks, a n d c o b a l t c o m p o u n d s a r e u s e d t o h a s t e n
the o x i d a t i o n a n d h e n c e t h e d r y i n g of o i l - b a s e d
p a i n t s . C o b a l t c o m p o u n d s a r e a l s o e m p l o y e d as
catalysts in a r a n g e of o r g a n i c r e a c t i o n s of w h i c h
the " O X O " (or h y d r o f o r m y l a t i o n ) r e a c t i o n a n d
hydrogιnation and dehydrogenation reactions are
the m o s t i m p o r t a n t ( p p . 1 1 3 4 - 6 ) .
O t h e r u s e s i n c l u d e t h e m a n u f a c t u r e of m a g ­
netic alloys. O f t h e s e t h e best k n o w n is " A l n i c o " ,
a steel c o n t a i n i n g , as its n a m e i m p l i e s , a l u m i n i u m
a n d n i c k e l , a s well a s cobalt. It is u s e d for per­
manent magnets which are u p to 25 times more
p o w e r f u l t h a n o r d i n a r y steel m a g n e t s .
A s a l r e a d y n o t e d ( p . 1073), t h e p l a t i n u m m e t ­
als a r e all isolated from c o n c e n t r a t e s o b t a i n e d
as " a n o d e s l i m e s " o r " c o n v e r t e r m a t t e . " In t h e
classical p r o c e s s , after r u t h e n i u m a n d o s m i u m
have been removed, excess oxidants are removed
b y b o i l i n g , i r i d i u m is p r e c i p i t a t e d as ( N H ^ I r C l τ
a n d r h o d i u m as [Rh(NH3) Cl]Cl2. In alternative
5
2 -
Spe­ s o l v e n t extraction p r o c e s s e s ( p . 1147) [ I r C ^ ]
is e x t r a c t e d in o r g a n i c a m i n e s leaving r h o d i u m
4th in t h e a q u e o u s p h a s e to b e precipitated, again,
as [Rh(NH3)5Cl]Cl2. In all c a s e s ignition in H 2
V6.2.3 Properties of the elements 1115

y i e l d s the m e t a l s as p o w d e r s or s p o n g e s w h i c h with the view, based on band-theory calculations,

c a n b e c o n s o l i d a t e d b y the t e c h n i q u e s of p o w d e r that the fee s t r u c t u r e is m o r e stable t h a n e i t h e r
metallurgy. b e c or h e p w h e n the o u t e r d orbitals are n e a r l y
In 1996, c o n s u m p t i o n in the w e s t e r n w o r l d w a s full. C o b a l t , t o o , h a s an a l l o t r o p e (the β-form)
14.2 t o n n e s of r h o d i u m a n d 3.8 t o n n e s of i r i d i u m . w i t h this s t r u c t u r e b u t this is o n l y stable a b o v e
U n q u e s t i o n a b l y t h e m a i n u s e s of r h o d i u m ( o v e r 4 1 7 ° C ; b e l o w this t e m p e r a t u r e t h e h e p α-form
9 0 % ) are n o w c a t a l y t i c , e.g. for t h e c o n t r o l of is t h e m o r e s t a b l e . H o w e v e r , the t r a n s f o r m a t i o n
e x h a u s t e m i s s i o n s in t h e c a r ( a u t o m o b i l e ) i n d u s t r y b e t w e e n t h e s e a l l o t r o p e s is g e n e r a l l y s l o w a n d the
a n d , in the f o r m of p h o s p h i n e c o m p l e x e s , in h y d r o ­ β - f o r m , w h i c h c a n b e stabilized b y the a d d i t i o n
g ι n a t i o n a n d h y d r o f o r m y l a t i o n r e a c t i o n s w h e r e it of a few per cent of iron, is often present
is frequently m o r e efficient t h a n the m o r e c o m ­ at r o o m t e m p e r a t u r e . T h i s , of c o u r s e , h a s an
m o n l y u s e d c o b a l t c a t a l y s t s . I r i d i u m is u s e d in t h e effect o n p h y s i c a l p r o p e r t i e s a n d is n o doubt
c o a t i n g of a n o d e s in c h l o r a l k a l i p l a n t a n d as a cat­ r e s p o n s i b l e for v a r i a t i o n s in r e p o r t e d v a l u e s for
alyst in the p r o d u c t i o n of a c e t i c a c i d . It a l s o finds s o m e p r o p e r t i e s e v e n in the c a s e of very p u r e

s m a l l - s c a l e a p p l i c a t i o n s in s p e c i a l i s t h a r d a l l o y s . c o b a l t . B y c o n t r a s t t h e a t o m i c w e i g h t s of c o b a l t
a n d r h o d i u m at least are k n o w n w i t h c o n s i d e r a b l e
precision, since these elements each have but
26.2.3 Properties of the elements o n e n a t u r a l l y o c c u r r i n g i s o t o p e . In the c a s e of
5 9
c o b a l t this is C o , but b o m b a r d m e n t by thermal
6 0
S o m e of t h e i m p o r t a n t p r o p e r t i e s of t h e s e t h r e e n e u t r o n s c o n v e r t s this t o t h e r a d i o a c t i v e Co.
e l e m e n t s are s u m m a r i z e d in T a b l e 2 6 . 1 . T h e latter h a s a half-life of 5.271 y a n d d e c a y s by
T h e m e t a l s a r e l u s t r o u s a n d silvery w i t h , in m e a n s of β~ a n d γ e m i s s i o n to n o n - r a d i o a c t i v e
6 0

the c a s e of c o b a l t , a b l u i s h t i n g e . R h o d i u m a n d N i . It is u s e d in m a n y fields of r e s e a r c h as
i r i d i u m are b o t h h a r d , c o b a l t less so b u t still a c o n c e n t r a t e d s o u r c e of y - r a d i a t i o n , a n d a l s o
a p p r e c i a b l y h a r d e r t h a n iron. R h o d i u m a n d Ir m e d i c a l l y in t h e t r e a t m e n t of m a l i g n a n t g r o w t h s .
1 9 1

h a v e fee s t r u c t u r e s , the first elements in the I r i d i u m h a s t w o stable i s o t o p e s : Ir 3 7 . 3 % a n d

, 9 3

transition series to d o s o ; this is in keeping I r 62.7%.

Table 26.1 Some properties of the elements cobalt, rhodium and iridium

Property Co Rh Ir

Atomic number 27 45 77
Number of naturally occurring 1 1 2
isotopes
Atomic weight 58.933200(9) 102.90550(2) 192.217(3)
8 1 14 7 2
Electronic configuration [Ar]3d 4s 7 2
[Kr]4d 5s [Xe]4f 5d 6s
Electronegativity 1.8 2.2 2.2
Metal radius (12-coordinate)/pm 125 134 135.5
Effective ionic radius
(6-coordinate)/pm V — 55 57
IV 53 60 62.5
III 54.5 (Is), 61 (hs) 66.5 68
II 65 (Is), 74.5 (hs) — —
MP/°C 1495 1960 2443
BP/°C 3100 3760 4550(±100)
Af/fus/klmor 1
16.3 21.6 26.4
Ai/vap/kJmol" 1
382 494 612(±13)
AHf (monatomic gas)/kJmol 1
425(±17) 556(±11) 669(±8)
Density (20 C)/gcirT o 3
8.90 12.39 22.56
Electrical resistivity ( 2 0 ° C ) ^ o h m c m 6.24 4.33 4.71
 1116 Cobalt, Rhodium and Iridium Ch. 26

T h e m p s , b p s a n d e n t h a l p i e s of a t o m i z a t i o n state. N o o x i d a t i o n states a r e f o u n d a b o v e +6
are l o w e r t h a n for t h e p r e c e d i n g e l e m e n t s in the for R h a n d Ir, o r a b o v e + 5 for C o . I n d e e d ,
p e r i o d i c t a b l e s , p r e s u m a b l y b e c a u s e t h e (n — l ) d e x a m p l e s of c o b a l t in - f 4 a n d + 5 a n d of r h o d i u m
e l e c t r o n s are b e i n g d r a w n i n c r e a s i n g l y i n t o t h e o r i r i d i u m in + 5 a n d + 6 o x i d a t i o n states are r a r e
inert e l e c t r o n c o r e s of t h e a t o m s . In t h e first series and sometimes poorly characterized.
C o , like its n e i g h b o u r s F e a n d N i , is f e r r o m a g ­ T h e m o s t c o m m o n o x i d a t i o n states of c o b a l t
netic (in b o t h a l l o t r o p i e f o r m s ) ; w h i l e it d o e s n o t are + 2 and + 3 . [ C o ( H 0 ) ] 2 6
2 +
and [ C o ( H 0 ) ] + 2 6
3

attain the h i g h s a t u r a t i o n m a g n e t i z a t i o n of iron, a r e b o t h k n o w n b u t t h e latter is a s t r o n g o x i d i z i n g

its C u r i e p o i n t ( > 1 1 0 0 ° C ) is m u c h h i g h e r t h a n a g e n t a n d in a q u e o u s s o l u t i o n , u n l e s s it is a c i d i c ,
that for F e ( 7 6 8 ° C ) . it d e c o m p o s e s r a p i d l y as t h e C o 1 1 1
oxidizes the
w a t e r w i t h e v o l u t i o n of o x y g e n . C o n s e q u e n t l y , in
1 1 1 1 1
contrast to C o , C o p r o v i d e s few s i m p l e salts,
26.2.4 Chemical reactivity and trends
and those which do occur are unstable. However,
1 1 1

C o b a l t is a p p r e c i a b l y less r e a c t i v e t h a n iron, a n d Co is u n s u r p a s s e d in t h e n u m b e r of c o o r d i n a ­
so c o n t r a s t s less m a r k e d l y w i t h t h e t w o h e a v i e r tion c o m p l e x e s w h i c h it f o r m s , e s p e c i a l l y w i t h
m e m b e r s of its triad. It is stable t o a t m o s p h e r i c iV-donor l i g a n d s . Virtually all of t h e s e c o m p l e x e s
o x y g e n u n l e s s h e a t e d , w h e n it is o x i d i z e d first t o are l o w - s p i n , t h e t\ g configuration producing a
C03O4; a b o v e 9 0 0 ° C t h e p r o d u c t is C o O w h i c h is particularly high C F S E (p. 1131).
a l s o p r o d u c e d b y t h e a c t i o n of s t e a m o n t h e r e d - T h e effect of t h e C F S E is e x p e c t e d t o be
h o t m e t a l . It d i s s o l v e s r a t h e r s l o w l y in dil m i n e r a l e v e n m o r e m a r k e d in t h e c a s e of t h e h e a v i e r
1 1
a c i d s g i v i n g salts of C o , a n d r e a c t s o n h e a t i n g elements because for them the crystal field
w i t h t h e h a l o g e n s a n d o t h e r n o n - m e t a l s s u c h as splittings a r e m u c h g r e a t e r . A s a r e s u l t t h e + 3
B , C , P , A s a n d S, b u t is u n r e a c t i v e t o H 2 and N . 2 state is t h e m o s t i m p o r t a n t o n e for b o t h R h a n d
3 +
Rhodium and iridium will also react with Ir a n d [ M ( H 0 ) 6 ] 2 are the only simple aquo
o x y g e n a n d h a l o g e n s at r e d - h e a t , b u t o n l y s l o w l y , ions formed by these elements. With 7r-acceptor
a n d t h e s e m e t a l s are e s p e c i a l l y n o t a b l e for their l i g a n d s t h e + 1 o x i d a t i o n state is a l s o w e l l k n o w n
extreme inertness to acids, even aqua regia. for R h a n d Ir. It is n o t i c e a b l e , h o w e v e r , that t h e
D i s s o l u t i o n of r h o d i u m m e t a l is b e s t effected similarity of t h e s e t w o h e a v i e r e l e m e n t s is less
b y fusion w i t h N a H S 0 , a p r o c e s s u s e d in its
4
t h a n is t h e c a s e e a r l i e r in t h e transition series
c o m m e r c i a l s e p a r a t i o n . In the c a s e of i r i d i u m , and, although rhodium resembles iridium more
oxidizing molten alkalis such as Na 0 2 2 or than cobalt, nevertheless there are significant
KOH + KNO3 will produce I r 0 2 which can then d i f f e r e n c e s . O n e e x a m p l e is p r o v i d e d b y t h e + 4
b e d i s s o l v e d in a q u a r e g i a . A l t e r n a t i v e l y , a r a t h e r o x i d a t i o n state w h i c h o c c u r s t o a n a p p r e c i a b l e
e x t r e m e m e a s u r e w h i c h is efficacious w i t h b o t h e x t e n t in i r i d i u m b u t n o t in r h o d i u m . ( T h e e a s e
m e t a l s , is to h e a t t h e m w i t h c o n e HC1 + N a C 1 0 3 with which Ir™ v
s
Ir 111
sometimes occurs
in a s e a l e d t u b e at 1 2 5 - 1 5 0 ° C . c a n b e a s o u r c e of a n n o y a n c e t o preparative
T a b l e 2 6 . 2 is a list of e x a m p l e s of c o m p o u n d s chemists.)
of t h e s e e l e m e n t s in v a r i o u s o x i d a t i o n states. Table 26.2 also reveals a diminished tendency
T h e m o s t striking feature of this, as c o m p a r e d on the part of these elements to form
t o t h e c o r r e s p o n d i n g lists for p r e c e d i n g t r i a d s , c o m p o u n d s of h i g h c o o r d i n a t i o n n u m b e r w h e n
is that for t h e first t i m e t h e r a n g e of o x i d a t i o n c o m p a r e d with the iron group and, apart from
states h a s d i m i n i s h e d . T h i s is a m a n i f e s t a t i o n of [Co(N03)4] ~, 2
a coordination number of 6
the i n c r e a s i n g stability of t h e (n — l ) d e l e c t r o n s , is rarely exceeded. There is also a marked
w h o s e attraction t o the a t o m i c n u c l e u s is n o w r e l u c t a n c e to f o r m o x o a n i o n s (p. 1118). T h i s is
sufficient to prevent the elements attaining p r e s u m a b l y b e c a u s e their f o r m a t i o n r e q u i r e s t h e
the h i g h e s t o x i d a t i o n states a n d so t o render d o n a t i o n of π e l e c t r o n s f r o m t h e o x y g e n a t o m s
i r r e l e v a n t t h e c o n c e p t of a " g r o u p " oxidation to the metal and the metals b e c o m e progressively
§26.3.1 Oxides and sulfides 1117

Table 26.2 Oxidation states and stereochemistries of some compounds of cobalt, rhodium and iridium

Oxidation Coordination
state number Stereochemistry Co Rh/Ir

-3 3 [Co(CO) ] " 3
3
[M(C0) ] " 3
3

- 1 (d ) 10
4 Tetrahedral [Co(CO) ]" 4 [Rh(CO) -, [lr(C0) (PPh )]- 4 3 3
9
0(d ) 4 Tetrahedral [Co(PMe ) ] 3 4

6 Octahedral [Co (CO) ]

2 8 [M (C0) ]
4 1 2

Kd ) 8
2 Linear [Co0 ] -
2
3

3 Planar (?) [RhCl(PCy ) ] 3 2

+
T-shaped [Rh(PPh ) ] 3 3

4 Square planar [RhCl(PPh ) ] 3 3

[lr(C0)Cl(PPh ) ] 3 2

5 Trigonal bipyramidal [Co(NCMe) ] 5

+
[RhH(PF ) ], 3 4

[Ir(C0)H(PPh ) ] 3 3

Square pyramidal [Co(NCPh) ] 5

+

6 Octahedral [Co(bipy) ]+ 3

7
2(d ) 2 Linear [Co{N(SiMe ) } ] 3 2 2

3 Planar [Co{N(SiMe ) } (PPh )] 3 2 2 3

4 Tetrahedral [CoCl ] - 4
2

Square planar [Co(phthalocyanine)] [RhCl {P(^-MeC H ) } ]

2 6 4 3 2

5 Trigonal bipyramidal [CoBr{N(C H NMe ) }]+ 2 4 2 3

3
Square pyramidal [Co(CN) ] " 5 [Rh (0 CMe) ]
2 2 4

6 Octahedral [Co(H 0 ] 2 6
2 +
[Rh (0 CMe) (H 0) ]
2 2 4 2 2

8 Dodecahedral [Co(N0 ) ] " 3 4

2

3(d ) 6
4 Tetrahedral [CoW O ] - 1 2 4 0
5

5 Trigonal bipyramidal [IrH (PR ) ]

3 3 2

Square pyramidal [Co(corrole)(PPh )] 3

(a)
[RhI Me(PPh ) ]
2 3 2

3 +
6 Octahedral [Co(NH ) ] 3 6 [MC1 ] - 6
3

5 (b)
4(d ) 4 Tetrahedral [Co(l-norbornyl) ] 4

2
6 Octahedral [CoF ] ~
6 [MC1 ] " 6
2

5(d ) 4
6 Octahedral [MF ]- 6

7 Pentagonal bipyramidal [IrH (PR ) ]

5 3 2

6(d ) 3
6 Octahedral [MF ] 6

( a )
C o r r o l e i s a tetrapyrrolic m a c r o c y c l e
( b )
l - N o r b o r n y l i s a bicyclo[2.2.1]hept-l-yl

less a b l e t o a c t a s π a c c e p t o r s a s their d orbitals 26.3.1 Oxides and sulfides

are filled.
H y d r i d o c o m p l e x e s of all t h r e e e l e m e n t s , a n d
c o v e r i n g a r a n g e of f o r m a l o x i d a t i o n s t a t e s , a r e
i m p o r t a n t b e c a u s e of their r o l e s in h o m o g e n e o u s
catalysis either as the catalysts themselves or as
i n t e r m e d i a t e s in t h e c a t a l y t i c c y c l e s .
26.3 Compounds of Cobalt,
Rhodium and Iridium
B i n a r y b o r i d e s ( p . 147) a n d c a r b i d e s ( p . 2 9 7 )
have been discussed already.
A s a r e s u l t of t h e d i m i n u t i o n in t h e r a n g e of o x i ­
d a t i o n states w h i c h h a s a l r e a d y b e e n m e n t i o n e d ,
t h e n u m b e r of o x i d e s f o r m e d b y t h e s e e l e m e n t s is
less t h a n in t h e p r e c e d i n g g r o u p s , b e i n g confined
t o t w o e a c h for c o b a l t ( C o O , C03O4) a n d r h o d i u m
(RI12O3, RI1O2) a n d t o j u s t o n e for i r i d i u m (Ι1Ό2)
(though an impure sesquioxide 1^03 has been
reported — see below). N o trioxides are known.
T h e o n l y o x i d e f o r m e d b y a n y of t h e s e m e t ­
als in t h e d i v a l e n t state is C o O ; this is p r e p a r e d
as a n o l i v e - g r e e n p o w d e r b y s t r o n g l y h e a t i n g t h e
m e t a l in air o r s t e a m , o r a l t e r n a t i v e l y b y h e a t i n g
1118 Cobalt, Rhodium and Iridium Ch. 26

the h y d r o x i d e , c a r b o n a t e or nitrate in the a b s e n c e o b t a i n e d by igniting K^IrClτ w i t h N a C U 3 or, as

of air. It h a s the rock-salt structure a n d is anti- its h y d r a t e , b y a d d i n g K O H to a q u e o u s K3[IrCl6]
f e r r o m a g n e t i c b e l o w 2 8 9 K. B y r e a c t i n g it with u n d e r CO2. H o w e v e r , e v e n if it is a true c o m ­
silica a n d a l u m i n a , p i g m e n t s a r e p r o d u c e d w h i c h p o u n d , it is a l w a y s i m p u r e a n d is readily o x i d i z e d
a r e used in the c e r a m i c s i n d u s t r y . C o O is stable to I r 0 . 2

in air at a m b i e n t t e m p e r a t u r e s a n d a b o v e 900° C O x o a n i o n s are r a r e in this g r o u p ; e x c e p t i o n s

b u t if h e a t e d at, say, 6 0 0 - 7 0 0 ° C , it is c o n v e r t e d v
i n c l u d e the u n s t a b l e [ C o 0 ] " a n d [ C o 0 ] - . 4
3 n
3
4

n
into the b l a c k C o 0 . T h i s is C o C o ^ 0
3 4 4and H e a t i n g m i x t u r e s of the a p p r o p r i a t e o x i d e s in
1 1
h a s the n o r m a l spinel structure with C o ions in oxygen, or under pressure, produces materials
1 1 1
t e t r a h e d r a l a n d C o in o c t a h e d r a l sites w i t h i n the w i t h the s t o i c h i o m e t r y , M3C0O4, w h i c h , together
c c p lattice of o x i d e i o n s . T h i s is to b e e x p e c t e d with their o x i d i z i n g p r o p e r t i e s , s u g g e s t s the p r e s ­
(p. 1080) b e c a u s e of the d o m i n a t i n g a d v a n t a g e of v
e n c e of C o . W h e n C o O is h e a t e d with 2.2 m o l e s
6
p l a c i n g the d ions in o c t a h e d r a l sites, w h e r e of N a 2 0 at 550° in a sealed t u b e u n d e r argon,
a d o p t i o n of the l o w - s p i n configuration g i v e s it a n
b r i g h t - r e d c r y s t a l s of N a C o 0 3 are f o r m e d . T h e
4

d e c i s i v e l y f a v o u r a b l e C F S E . T h e ability of C03O4 compound hydrolyses immediately on contact

to a b s o r b o x y g e n , a n d p o s s i b l y also the r e t e n ­ w i t h a t m o s p h e r i c m o i s t u r e a n d is n o t a b l e in c o n ­
4
tion of w a t e r in p r e p a r a t i o n s from the h y d r o x i d e , taining discrete planar [C0O3] " ions reminiscent
h a v e led to c l a i m s for the e x i s t e n c e of C02O3, of the c a r b o n a t e ion ( C o - Ο 1 8 6 z b 6 p m ) a n d is
but it is doubtful if t h e s e c l a i m s are valid. O x i ­ s i m i l a r to t h e r e d o x o f e r r a t e ( I I ) , N a [ F e 0 3 ] . T h e 4

dation of Co(OH)2, or addition of a q u e o u s alkali l u s t r o u s r e d tetracobaltate(II) N a i o f C o ^ O ^ , with

to a cobalt(III) c o m p l e x , p r o d u c e s a d a r k - b r o w n an a n i o n a n a l o g o u s to t h e cfltefta-tetracarbonate
material w h i c h o n d r y i n g at 150°C in fact g i v e s [QOη] 2 -
, is a l s o k n o w n . F o r iridium, p r o l o n g e d
cobalt(IU) oxide hydroxide, C o O ( O H ) . heating of Ir02 and L12O produces Li2ir03
H e a t i n g r h o d i u m m e t a l o r the trichloride w h i c h , w h e n h e a t e d with 2.2 m o l e s of N a 2 0 at
in o x y g e n at 6 0 0 ° C , or s i m p l y h e a t i n g t h e 8 0 0 ° C for 71 d a y s , g i v e s t r a n s p a r e n t red crystals
trinitrate, p r o d u c e s d a r k - g r e y R112O3 w h i c h h a s of N a I r 0
4 4 in w h i c h the I r ( I V ) is s u r r o u n d e d by
2 ( 4 )
the c o r u n d u m structure (p. 2 4 2 ) ; it is t h e o n l y four O " in a s q u a r e ( I r - 0 = 190.2 p m . )
stable o x i d e f o r m e d b y this m e t a l . T h e y e l l o w A larger number of sulfides have been
precipitate f o r m e d b y the addition of alkali to r e p o r t e d b u t not all of t h e m h a v e b e e n fully
a q u e o u s solutions of r h o d i u m ( I I I ) is actually c h a r a c t e r i z e d . C o b a l t g i v e s rise to C0S2 with
R h 2 0 3 . 5 H 2 0 r a t h e r than a g e n u i n e h y d r o x i d e . the pyrites structure (p. 6 8 0 ) , Co3S with the
4
m
E l e c t r o l y t i c o x i d a t i o n of R h solutions a n d spinel structure (p. 2 4 7 ) , and Coi^S which
a d d i t i o n of alkali g i v e s a y e l l o w p r e c i p i t a t e h a s the N i A s structure (p. 5 5 5 ) a n d is c o b a l t -
o f Rh02-2H20, b u t a t t e m p t s to d e h y d r a t e this deficient. All are m e t a l l i c , as is CoηSg and
p r o d u c e R h 0 3 . B l a c k a n h y d r o u s RhU2 is b e s t
2 t h e c o r r e s p o n d i n g s e l e n i d e s a n d tellurides. T h e
o b t a i n e d b y h e a t i n g RI12O3 in o x y g e n u n d e r sulfides of rhodium and iridium are notable
p r e s s u r e ; it h a s the rutile structure, b u t it is not mainly for their inertness especially towards
well c h a r a c t e r i z e d . a c i d s , a n d m o s t of t h e m a r e semiconductors.
F o r i r i d i u m t h e p o s i t i o n is r e v e r s e d . T h i s t i m e T h e y a r e t h e disulfides MS2, o b t a i n e d from t h e
it is t h e b l a c k d i o x i d e , IrU2, w i t h t h e rutile s t r u c ­ e l e m e n t s ; the " s e s q u i s u l f i d e s " M2S3, obtained
ture (p. 9 6 1 ) , w h i c h is the o n l y definitely e s t a b ­ b y p a s s i n g H2S t h r o u g h a q u e o u s solutions of
lished o x i d e . It is o b t a i n e d b y h e a t i n g the m e t a l m
M ; a n d R h S s a n d IrS3, o b t a i n e d b y h e a t i n g
2

in o x y g e n or b y d e h y d r a t i n g t h e p r e c i p i t a t e p r o ­ MCI3 + S at 6 0 0 ° C . N u m e r o u s n o n s t o i c h i o m e t r i c
d u c e d w h e n alkali is a d d e d to an a q u e o u s solu­ s e l e n i d e s a n d tellurides are a l s o k n o w n .
2 -
tion of [ I r C ^ ] . C o n t a m i n a t i o n e i t h e r b y u n r e -
a c t e d m e t a l or b y * alkali is, h o w e v e r , difficult 4
K . M A D E R A N D a n d R . H O P P E , Z. anorg. allg. Chem. 619,
to a v o i d . T h e o t h e r o x i d e , 1^03, is said to b e 1 6 4 7 - 5 4 (1993).
§26.3.2 Halides 1119

Table 26.3 Halides of cobalt, rhodium and iridium (mp/°C)

Oxidation
state Fluorides Chlorides Bromides Iodides

+6 RhF 6

black (70°)
IrF 6

yellow (44°)
bp 53°
+5 [RhF ] 5 4

dark red
[IrF ] 5 4

yellow (104°)
+4 CoF 4

RhF 4

purple-red
IrF 4 I1CI4? IrBr ?
4 I1I4?
dark brown
+3 CoF 3

light brown
RhF 3 RhCl 3 RhBr 3 Rhl 3

red red red-brown black

IrF 3
IrCl 3 IrBr 3 M 3

black red red-brown dark brown

+2 CoF 2 CoCl 2 CoBr 2
CoI a 2

pink (1200°) blue (724°) green (678°) blue-black (515°)

B e c a u s e of p o s s i b l e catalytic a n d biological s h o w n o less t h a n 8 3 g a s e o u s i o n s r a n g i n g f r o m

r e l e v a n c e of m e t a l - s u l f u r c l u s t e r s , several s u c h [ C o S ] - to [ C o
2 3 8 S 2 4 ]-.
c o m p o u n d s of c o b a l t h a v e b e e n p r e p a r e d . T h e
action of H S o r M S 2 2 ( M = alkali m e t a l ) on
a n o n - a q u e o u s solution of a c o n v e n i e n t c o b a l t 26.3.2 Halides
c o m p o u n d (often c o n t a i n i n g , or in the p r e s e n c e
of, a p h o s p h i n e ) is a typical r o u t e . D i a m a g n e t i c T h e k n o w n h a l i d e s of this triad are listed in
[ C o S ( P R ) ] (R = Et, P h ) c o m p r i s e an o c t a h e ­
6 8 3 6
Table 2 6 . 3 . It c a n b e seen that, apart from C0F3,
dral array of m e t a l a t o m s ( C o - C o in the r a n g e CoF 4 a n d the doubtful iridium t e t r a h a l i d e s , they
2 8 1 . 7 to 2 8 9 . 4 p m ) , all faces c a p p e d b y /z -S fall into t h r e e c a t e g o r i e s :
3

( 5 )
atoms, a n d s h o w facile r e d o x b e h a v i o u r
(a) h i g h e r fluorides of Ir a n d R h ;
(b) a full c o m p l e m e n t of trihalides of Ir a n d
+
[Co S (PR ) ]6 8 3 6 [Co S (PR ) ]
6 8 3 6 Rh;
(c) d i h a l i d e s of c o b a l t
A n indication of the r a n g e of s u c h clusters
w h i c h m i g h t p o s s i b l y b e s y n t h e s i z e d is g i v e n T h e o c t a h e d r a l h e x a f l u o r i d e s are o b t a i n e d
b y the o b s e r v a t i o n (6)
that mass spectroscopic directly from the e l e m e n t s a n d b o t h are volatile,
e x t r e m e l y r e a c t i v e a n d c o r r o s i v e solids, R h F 6
a n a l y s i s of the p r o d u c t s of l a s e r - a b l a t i o n of C o S
b e i n g the least stable of the p l a t i n u m m e t a l
h e x a f l u o r i d e s a n d r e a c t i n g with g l a s s e v e n w h e n
5
M. HONG, Z. HUANG, X . LEI, G. WEI, B. KANG and
carefully d r i e d . T h e y are t h e r m a l l y u n s t a b l e a n d
H . L i u , Polyhedron, 10, 9 2 7 - 3 4 (1991).
6
J . E L N A K A T , K . J . F I S H E R , I. G . D A N C E and G. D. WILLET,
m u s t b e frozen out from the hot g a s e o u s r e a c t i o n
Inorg. Chem. 32 1 9 3 1 - 4 0 (1993). mixtures, otherwise they dissociate.
1120 Cobalt, Rhodium and Iridium Ch. 26

The pentafluorides of R h a n d I r m a y b e water-soluble hydrates can be produced by wet

prepared b y the deliberate thermal dissociation of methods. R h F . 6 H 0 3 2 and R h F . 9 H 0
3 2 can be
111
t h e h e x a f l u o r i d e s . T h e y also a r e h i g h l y r e a c t i v e i s o l a t e d f r o m a q u e o u s s o l u t i o n s of R h acidified
a n d a r e r e s p e c t i v e l y d a r k - r e d a n d y e l l o w solids, with H F . Their aqueous solutions are yellow,
w i t h t h e s a m e t e t r a m e r i c s t r u c t u r e a s [RuF5]4 a n d p o s s i b l y d u e t o t h e p r e s e n c e of [ R h ( H 0 ) 6 ] 2
3 +
.
[OsF ] 5 4 ( p . 1083). The dark-red deliquescent R h C l . 3 H 0 3 2 is t h e
RhF 4 is a p u r p l e - r e d solid, u s u a l l y p r e p a r e d b y most c o m m o n c o m p o u n d of rhodium and the
the r e a c t i o n of t h e s t r o n g fluorinating a g e n t BrF3 u s u a l starting p o i n t for t h e p r e p a r a t i o n of o t h e r
on R h B r . T h e corresponding compound I r F has
3 4 r h o d i u m c o m p o u n d s , a n d is itself b e s t p r e p a r e d
(7)
had an intriguing and instructive h i s t o r y . It w a s f r o m t h e m e t a l s p o n g e . T h i s is h e a t e d w i t h KC1
first c l a i m e d in 1 9 2 9 a n d a g a i n in 1 9 5 6 b u t this in a s t r e a m o f C l a n d t h e p r o d u c t e x t r a c t e d w i t h
2

m a t e r i a l w a s s h o w n in 1965 t o b e , in reality, t h e water. T h e solution contains K [Rh(H 0)Cl5]

2 2

p r e v i o u s l y u n k n o w n Ιτ¥$. I r F c a n n o w b e m a d e
4 and treatment with K O H precipitates the hydrous
( 1 9 7 4 ) b y r e d u c i n g lrF$ w i t h t h e s t o i c h i o m e t r i c Rh 0 2 3 w h i c h c a n b e d i s s o l v e d in h y d r o c h l o r i c
amount of iridium-black: acid a n d the solution evaporated to dryness.
400° R h B r . 2 H 0 a l s o is f o r m e d f r o m t h e m e t a l b y
3 2

4 I r F + Ir 5 • 5IrF 4 t r e a t i n g it w i t h h y d r o c h l o r i c a c i d a n d b r o m i n e .
T h e i r i d i u m trihalides a r e r a t h e r s i m i l a r t o
The dark-brown product disproportionates above
t h o s e of r h o d i u m . A n h y d r o u s I r F is o b t a i n e d
400° into I r F 3 a n d t h e volatile lrF$. T h e s t r u c ­ 3

t u r e features {IrF6} o c t a h e d r a w h i c h s h a r e 4 F b y r e d u c i n g IrFτ w i t h t h e m e t a l , I r C l 3 and IrBr 3

a t o m s , e a c h w i t h o n e o t h e r {IrFe} g r o u p , l e a v i n g by heating the elements, and I r l 3 b y h e a t i n g its

a p a i r o f cis v e r t i c e s u n s h a r e d : this is e s s e n t i a l l y h y d r a t e in vacuo. W a t e r - s o l u b l e h y d r a t e s of t h e
a rutile t y p e s t r u c t u r e ( p . 9 6 1 ) f r o m w h i c h alter­ tri-chloride, -bromide, a n d -iodide are produced
nate metal atoms have been removed from each by dissolving hydrous l r 0 2 3 in t h e a p p r o p r i a t e
e d g e - s h a r i n g c h a i n . It w a s t h e first 3 D s t r u c t u r e a c i d a n d , like its r h o d i u m a n a l o g u e , I r C l . 3 H 0 3 2

to h a v e b e e n f o u n d for a t e t r a f l u o r i d e . (7)
Claims p r o v i d e s a c o n v e n i e n t starting p o i n t in i r i d i u m
h a v e b e e n m a d e for t h e isolation o f all t h e o t h e r chemistry.
i r i d i u m t e t r a h a l i d e s , b u t t h e r e is s o m e d o u b t a s L o w e r h a l i d e s of R h a n d I r h a v e b e e n r e p o r t e d
to w h e t h e r t h e s e c a n b e s u b s t a n t i a t e d . T h i s is a n and, whilst their e x i s t e n c e cannot be denied
u n e x p e c t e d situation s i n c e + 4 is o n e o f i r i d i u m ' s w i t h c e r t a i n t y , further s u b s t a n t i a t i o n is n e e d e d .
c o m m o n o x i d a t i o n states and, i n d e e d , t h e d e r i v e d U n q u e s t i o n a b l y , t h e d i v a l e n t state is t h e p r e s e r v e
anions [ I r X o ] 2 -
(X = F, CI, Br) are well known. of c o b a l t . Apart from the strongly oxidizing
The most familiar and most stable of t h e C0F3 (a light-brown p o w d e r isomorphous with
h a l i d e s o f R h a n d Ir, h o w e v e r , a r e t h e t r i h a l i d e s . FeCl 3 and the product of the action of F 2

(8)
T h o s e of R h r a n g e in c o l o u r from t h e r e d R h F 3
on C o C l 2 at 2 5 0 ° C ) a n d C o F 4 (identified in
to b l a c k R h l 3 a n d , apart f r o m t h e latter, w h i c h the gaseous phase by mass spectometry, as the
is o b t a i n e d b y t h e a c t i o n of a q u e o u s KI on singly c h a r g e d c a t i o n , w h e n C o F 3 and T b F are 4

the tribromide, they m a y be obtained in t h e heated to 6 0 0 - 6 8 0 K), the only k n o w n halides

a n h y d r o u s state directly f r o m t h e e l e m e n t s . R h F 3
h a s a structure s i m i l a r t o that of R e 0 3 ( p . 1047),
w h i l e R h C l is i s o m o r p h o u s w i t h A1C1 ( p . 2 3 4 ) .
3 3
of c o b a l t a r e t h e d i h a l i d e s . I n all o f t h e s e t h e
c o b a l t is o c t a h e d r a l l y c o o r d i n a t e d . T h e a n h y d r o u s
compounds are prepared by dry methods: C o F 2

T h e anhydrous trihalides are generally unreactive (pink) by heating C o C l in H F ; C o C l 2 2 (blue) a n d

a n d i n s o l u b l e in w a t e r b u t , e x c e p t i n g t h e t r i - CoBr 2 ( g r e e n ) b y t h e a c t i o n of t h e h a l o g e n s o n
iodide which is o n l y known in this form, the h e a t e d m e t a l ; C o I 2 ( b l u e - b l a c k ) b y t h e action

8
7
N . B A R T L E T T and A . T R E S S A U D , Comptes Rendus 278C, M. V. KOBOROV, L. N. SAVINOVA and L. N . SIDEROV, J.
1 5 0 1 - 4 (1974). Chem. Thermodynam. 2 5 , 1 1 6 1 - 8 (1993).
§26.3.3
of H I o n t h e h e a t e d m e t a l . T h e fluoride is o n l y
slightly s o l u b l e i n w a t e r b u t t h e o t h e r s d i s s o l v e
readily t o g i v e s o l u t i o n s f r o m w h i c h p i n k o r r e d
h e x a h y d r a t e s c a n b e c r y s t a l l i z e d . T h e s e solutions
c a n alternatively a n d m o r e c o n v e n i e n t l y b e m a d e
b y d i s s o l v i n g t h e m e t a l , o x i d e o r c a r b o n a t e in
the a p p r o p r i a t e h y d r o h a l i c acid. T h e c h l o r i d e is
w i d e l y u s e d a s a n i n d i c a t o r in t h e d e s i c c a n t , silica
gel, since its b l u e a n h y d r o u s f o r m t u r n s p i n k a s
it h y d r a t e s ( s e e p . 1131).
T h e disinclination of these metals t o form
oxoanions h a s already been remarked a n d the
s a m e is e v i d e n t l y true o f o x o h a l i d e s : n o n e h a v e
been authenticated.
26.3.3 Complexes
T h e c h e m i s t r y o f o x i d a t i o n states a b o v e I V i s
s p a r s e . A p a r t from RhF6 a n d IrF6, s u c h c h e m i s t r y
as t h e r e i s , i s m a i n l y confined t o salts of [ R h F τ ]
and [IrFo]". These are prepared respectively
b y t h e a c t i o n o f F2 o n RI1CI3 a n d K F u n d e r
(9)
p r e s s u r e , a n d b y fluorinating a l o w e r h a l i d e o f
i r i d i u m w i t h BrF3 in t h e p r e s e n c e o f a h a l i d e
of t h e c o u n t e r c a t i o n . H y d r i d o c o m p l e x e s o f
i r i d i u m in t h e f o r m a l o x i d a t i o n state V a r e
o b t a i n e d b y t h e a c t i o n o f L1AIH4 o r L1BH4 o n
m
Ir c o m p o u n d s in t h e p r e s e n c e o f p h o s p h i n e
or c y c l o p e n t a d i e n y l l i g a n d s . [IrH5(PR3)2], in
w h i c h t h e five h y d r o g e n s l i e e q u a t o r i a l l y in a
pentagonal bipyramid, a n d the "half sandwich",
5
[(?7 -C5JMe5)IrH4], a r e e x a m p l e s .
Oxidation state IV ( d ) 5
C o b a l t p r o v i d e s o n l y a f e w e x a m p l e s o f this
o x i d a t i o n state, n a m e l y s o m e fluoro c o m p o u n d s
a n d m i x e d m e t a l o x i d e s , w h o s e purity is
questionable and, most notably, the thermally
stable, b r o w n , tetraalkyl, [Co(l-norbornyl)4].
P r e p a r e d b y t h e r e a c t i o n o f C0CI2 a n d L i ( l -
n o r b o r n y l ) , it is t h e o n l y o n e o f a series o f s u c h
c o m p o u n d s o b t a i n e d f o r t h e first r o w transition
9
A . K . BRISDON, J. H . HOLLOWAY, E . G . HOPE
W. L E V A S O N , Polyhedron 11, 7 - 1 1 ( 1 9 9 2 ) .
Complexes 1121
m e t a l s T i t o C o w h i c h h a s b e e n structurally
1
c h a r a c t e r i z e d / ^ It is t e t r a h e d r a l a n d , w i t h a
5
d configuration, its r o o m - t e m p e r a t u r e m a g n e t i c
m o m e n t of 1.89 B M i n d i c a t e s that it is l o w -
spin; t h e first e x a m p l e t o b e a u t h e n t i c a t e d for a
t e t r a h e d r a l c o m p l e x o f a first r o w transition m e t a l .
R h o d i u m ( I V ) c o m p l e x e s a r e confined t o salts o f
2 -
the o x i d i z i n g a n d r e a d i l y h y d r o l y s e d [ R h X τ ]
( X = F , C l ) , t h e g r e e n solid Cs2[RhCl6] b e i n g o n e
1 1 )
of t h e f e w t o b e c o n f i r m e d / Only iridium(IV)
s h o w s a p p r e c i a b l e stability.
2
T h e salts o f [ I r X ] " ( X = F , C I , B r ) a r e
6
c o m p a r a t i v e l y stable a n d their c o l o u r d e e p e n s
from red, through reddish-black to bluish-black
with increasing atomic weight of the halogen.
2 -
[ I r F τ ] " is o b t a i n e d b y r e d u c t i o n o f [ I r F o ] ,
2 - 3 -
[ I r C l o ] b y o x i d a t i o n of [ I r C l o ] with c h l o r i n e ,
2 2
a n d [ I r B r ] ~ b y B r " substitution o f [ I r C l ] ~
6 6
in a q u e o u s solution. T h e h e x a c h l o r o i r i d a t e s
-
in p a r t i c u l a r h a v e b e e n t h e subject o f m a n y
magnetic investigations. They have magnetic
m o m e n t s at r o o m t e m p e r a t u r e s o m e w h a t b e l o w
t h e s p i n - o n l y v a l u e f o r t h e t\ configuration g
( 1 . 7 3 B M ) , a n d this falls w i t h t e m p e r a t u r e .
T h i s h a s b e e n i n t e r p r e t e d a s t h e result o f
a n t i f e r r o m a g n e t i c interaction o p e r a t i n g b y a
superexchange mechanism between adjacent
I V
Ir ions via intervening chlorine atoms.
M o r e i m p o r t a n t l y , i n 1 9 5 3 in a short b u t
( 1 2 )
classic p a p e r , J. O w e n a n d K . W . H . S t e v e n s
r e p o r t e d t h e o b s e r v a t i o n o f hyperfine structure
in t h e e s r signal o b t a i n e d from solid solutions
of (NH4)2[IrCl6] in t h e i s o m o r p h o u s , b u t
d i a m a g n e t i c , (NH4)2[PtCl6]. T h i s arises f r o m t h e
influence o f t h e c h l o r i n e n u c l e i a n d , from t h e
m a g n i t u d e of t h e splitting, it w a s inferred that t h e
single unpaired electron, which is ostensibly o n e
5
of t h e m e t a l d e l e c t r o n s , in fact s p e n d s o n l y 8 0 %
of its t i m e o n t h e m e t a l , t h e rest o f t h e t i m e b e i n g
divided equally between the 6 chlorine ligands.
T h i s w a s t h e first u n a m b i g u o u s e v i d e n c e that
m e t a l d e l e c t r o n s a r e a b l e t o m o v e in m o l e c u l a r
1 0
Ε. K . B Y R N E , D . S . RICHESON and K . H . THEOPOLD, J.
Chem. Soc, Chem. Commun., 1491-2 (1986).
1 1
1. J . E L L I S O N a n d R . D . G I L L A R D , Polyhedron 15, 3 3 9 - 4 8
and (1996).
1 2
J . O W E N a n d K . W . H . S T E V E N S , Nature 171, 8 3 6 ( 1 9 5 3 ) .
1122 Cobalt, Rhodium and Iridium Ch. 26

Table 26.4 E° for some C o / C o I H n couples in acid solution

Couple £7V

[ C o ( H 0 ) ] + e" 2 6 3 + [Co(H 0) ] 2 6 2 + l .83

[Co(C 0 )3] " + e " ^ = ±
2 4 3 [Co(C 0 ) ] ~ 2 4 3 4 0.57
[Co(edta)]" + e " [Co(edta)] " 2 0.37
[Coibipy),]^ + e " ^ = ^ [Co(bipy),] 2+ 0.31
[Co(en),] + e " ^ = ± 3+ [Co(en) ] 3 2+ 0.18
[Co(NH ) ] + e - ^ = ^ 3 6 3 + [Co(NH ) ] 3 6 2 + 0.108
[Co(CN) ] ~ + H 0 + e" ^ = = ±
6 3 2 [Co(CN) (H 0)] " + CN" 5 2 3 -0.8
\0 + 2 H + 2 e - ^ = ^
2 + H 0 2 1.229

Oxidation state III ( d ) 6

F o r all t h r e e e l e m e n t s this is the m o s t prolific

oxidation state, p r o v i d i n g a wide variety of
k i n e t i c a l l y inert c o m p l e x e s . A s h a s a l r e a d y b e e n
pointed out, these are virtually all low-spin
and octahedral, a major stabilizing influence
b e i n g the h i g h C F S E a s s o c i a t e d w i t h the t\ g

c o n f i g u r a t i o n ( y A , the m a x i m u m p o s s i b l e for
G

any d* c o n f i g u r a t i o n ) . Even [Co(H20)6] 3 + is

F i g u r e 26.1
Trinuclear structure of l o w - s p i n b u t it is s u c h a p o w e r f u l oxidizing
(i) [ I r , 0 ( S 0 ) 9 l
4 1 ( ) _ and a g e n t that it is u n s t a b l e in a q u e o u s solutions
(ii) [ I r N ( S 0 ) 6 ( H 0 ) ] - .
3 4 2 3 4 a n d o n l y a few s i m p l e salt h y d r a t e s , s u c h as the
blue C o ( S 0 ) . 1 8 H 0 and 2 4 3 2 MCo(S0 ) .12H 0 4 2 2

( Μ = K, Rb, Cs, NH ), 4 which contain the

orbitals o v e r the w h o l e c o m p l e x , a n d i m p l i e s the
p r e s e n c e of π as well as σ b o n d i n g . h e x a a q u o ion, a n d C o F . 3 | H 2 0 c a n b e isolated. 3

This paucity of simple salts of cobalt(III)

In a q u e o u s solution, the h a l i d e i o n s of [ I r X o ] 2 -

m a y b e r e p l a c e d by solvent a n d a n u m b e r of c o n t r a s t s s h a r p l y with the g r e a t a b u n d a n c e of its

a q u o substituted d e r i v a t i v e s h a v e b e e n r e p o r t e d . complexes, expecially with N - d o n o r l i g a n d s ( 1 3 ) ,

Other lr I V complexes with 0-donor ligands a n d it is e v i d e n t that the h i g h C F S E is n o t t h e
are [ I r 0 ( C 0 ) ] ~ , o b t a i n e d by o x i d i z i n g Ir
4 2 4 2 111
o n l y factor affecting the stability of this o x i d a t i o n
o x a l a t o c o m p l e x e s with c h l o r i n e , a n d N a 2 i r 0 , 3
state.
o b t a i n e d by fusing Ir a n d N a 2 C 0 . 3 T a b l e 2 6 . 4 illustrates t h e r e m a r k a b l e sensitivity
T w o interesting t r i n u c l e a r c o m p l e x e s m u s t a l s o of the r e d u c t i o n p o t e n t i a l of the C o 1 1 1 /Co 1 1 couple
b e m e n t i o n e d . T h e y are K i o [ I r 0 ( S 0 ) 9 ] . 3 H 2 0 , 3 4 to different l i g a n d s w h o s e p r e s e n c e r e n d e r s C o 1 1

obtained by boiling Na IrCl6 2 and K2S0 4 in u n s t a b l e to aerial o x i d a t i o n . T h e e x t r e m e effect

c o n e sulfuric acid, a n d K4[Ir3N(S0 ) (H 0)3], 4 6 2 of C N - c a n b e t h o u g h t of as b e i n g d u e , o n
obtained by boiling Na IrCl6 3 and (NH )2S0 4 4 the o n e h a n d , t o the ability of its e m p t y π*
in c o n e sulfuric acid. T h e y h a v e t h e s t r u c t u r e o r b i t a l s to a c c e p t " b a c k - d o n a t e d " c h a r g e f r o m the
shown in Fig. 2 6 . 1 , analogous to that of m e t a l ' s filled ti g orbitals a n d , o n t h e other, to
the b a s i c c a r b o x y l a t e s , [ M ^ O ^ C R ^ ] * (see its effectiveness as a σ d o n o r ( e n h a n c e d partly
Fig. 2 3 . 9 ) . T h e o x o s p e c i e s f o r m a l l y contains b y its n e g a t i v e c h a r g e ) . T h e m a g n i t u d e s of the
1 Ir I V a n d 2 Ir 111 i o n s a n d the nitride s p e c i e s 2 I r I V

ions and 1 I r H I ion, b u t in e a c h c a s e the c h a r g e s 1 3 P . H E N D R Y and A . L U D I , Adv. Inorg. Chem. 35, 117-98
are p r o b a b l y d e l o c a l i z e d o v e r the w h o l e c o m p l e x . (1990).
§26.3.3
c h a n g e s in E° are e v e n g r e a t e r t h a n t h o s e n o t e d
m n
for the F e / F e c o u p l e (p. 1093), t h o u g h if the
t w o s y s t e m s are c o m p a r e d it m u s t b e r e m e m b e r e d
that t h e o x i d a t i o n state w h i c h c a n b e stabilized by
a d o p t i o n of the l o w - s p i n t\ configuration is + 3
for c o b a l t b u t o n l y + 2 for iron. N e v e r t h e l e s s , the
effect of i n c r e a s i n g p H is c l o s e l y similar, the M
" h y d r o x i d e " of b o t h m e t a l s b e i n g far less s o l u b l e
n
t h a n the M " h y d r o x i d e " . In t h e c a s e of c o b a l t
this r e d u c e s E° from 1.83 to 0.17 V :
m H
C o O ( O H ) + H 0 + e" = = ^ Co (OH) + OH";
2 2
E° = 0.17 V
t h e r e b y facilitating o x i d a t i o n to the + 3 state.
C o m p l e x e s of cobalt(III), like t h o s e of
c h r o m i u m ( I I I ) (p. 1027), are kinetically inert a n d
so, again, indirect m e t h o d s of p r e p a r a t i o n are to
b e preferred. M o s t c o m m o n l y the l i g a n d is a d d e d
to an a q u e o u s solution of an a p p r o p r i a t e salt
of c o b a l t ( I I ) , a n d the c o b a l t ( I I ) c o m p l e x t h e r e b y
f o r m e d is o x i d i z e d b y s o m e c o n v e n i e n t o x i d a n t ,
frequently (if an TV-donor l i g a n d is i n v o l v e d ) in
the p r e s e n c e of a catalyst s u c h as active c h a r c o a l .
M o l e c u l a r o x y g e n is often u s e d as the o x i d a n t
s i m p l y b y d r a w i n g a s t r e a m of air t h r o u g h the
solution for a few h o u r s , b u t t h e s a m e result c a n ,
in m a n y c a s e s , b e o b t a i n e d m o r e q u i c k l y b y u s i n g
a q u e o u s solutions of H2O2.
T h e c o b a l t a m m i n e s , w h o s e n u m b e r is legion,
w e r e a m o n g s t t h e first c o o r d i n a t i o n c o m p o u n d s to
b e s y s t e m a t i c a l l y s t u d i e d ^ a n d are u n d o u b t e d l y
the m o s t e x t e n s i v e l y i n v e s t i g a t e d class of
cobalt(III) c o m p l e x . O x i d a t i o n of aqueous
m i x t u r e s of C o X , N H X a n d N H ( X = CI,
2 4 3
Br, NO3, etc.) c a n , b y v a r y i n g the c o n d i t i o n s
a n d particularly the relative p r o p o r t i o n s of the
r e a c t a n t s , b e u s e d to p r e p a r e c o m p l e x e s of
3
t y p e s s u c h as [ C o ( N H ) ] + , [ C o ( N H ) X ] + a n d 2 cobaltinitrite", N a [ C o ( N 0 2 ) o ] , a q u e o u s solu­
3 6 3 5
+
[ C o ( N H ) X 2 ] . T h e r a n g e of t h e s e c o m p o u n d s
3 4
^ T h e o b s e r v a t i o n b y Β . M . Tassaert in 1 7 9 8 that s o l u t i o n s
o f c o b a l t ( I I ) c h l o r i d e in a q u e o u s a m m o n i a g r a d u a l l y turn
b r o w n in air, a n d t h e n w i n e - r e d o n b e i n g b o i l e d , is g e n e r a l l y
a c c e p t e d a s the first preparation o f a c o b a l t ( I I I ) c o m p l e x . It
w a s r e a l i z e d later that m o r e than o n e c o m p l e x w a s i n v o l v e d
a n d that, b y v a r y i n g the r e l a t i v e c o n c e n t r a t i o n s o f a m m o n i a
a n d c h l o r i d e i o n , the c o m p l e x e s C0CI3 .JCNH3 (x = 6, 5 a n d
4) could be separated.
Complexes 1123
is further e x t e n d e d b y the r e p l a c e m e n t of X b y
o t h e r a n i o n i c o r n e u t r a l l i g a n d s . T h e inertness of
the c o m p o u n d s m a k e s s u c h substitution r e a c t i o n s
s l o w ( t a k i n g h o u r s o r d a y s to attain e q u i l i b r i u m )
and, b e i n g therefore a m e n a b l e to e x a m i n a t i o n
b y c o n v e n t i o n a l analytical t e c h n i q u e s , they h a v e
m
p r o v i d e d a c o n t i n u i n g focus for kinetic studies.
T h e forward (aquation) and backward (anation)
r e a c t i o n s of t h e p e n t a a m m i n e s :
2 +
[Co(NH ) X] 3 5 + H 0==^
2
3 +
[Co(NH ) (H 0)] 3 5 2 +X-
m u s t b e the m o s t t h o r o u g h l y studied substitution
r e a c t i o n s , c e r t a i n l y of o c t a h e d r a l c o m p o u n d s .
F u r t h e r m o r e , t h e isolation of cis a n d trans
i s o m e r s of the t e t r a a m m i n e s (p. 9 1 4 ) w a s an
i m p o r t a n t part of W e r n e r ' s classical p r o o f of the
o c t a h e d r a l structure of 6 - c o o r d i n a t e c o m p l e x e s .
T h e kinetic i n e r t n e s s of cobalt(III) w a s also
e x p l o i t e d b y H . T a u b e to d e m o n s t r a t e the inner-
s p h e r e m e c h a n i s m of e l e c t r o n transfer (see P a n e l
o n p . 1124).
C o m p o u n d s a n a l o g o u s to the c o b a l t a m m i n e s
m a y b e similarly o b t a i n e d u s i n g c h e l a t i n g a m i n e s
s u c h as e t h y t h e n e d i a m i n e o r b i p y r i d y l , a n d t h e s e
t o o h a v e p l a y e d an i m p o r t a n t role in s t e r e o ­
2 +
c h e m i c a l studies. T h u s d s - [ C o ( e n ) 2 ( N H ) C l ] 3
w a s r e s o l v e d into a n d /(—) optical iso­
m e r s b y W e r n e r in 1911 t h e r e b y d e m o n s t r a t ­
ing, to all b u t the m o s t d e t e r m i n e d d o u b t e r s ,
its o c t a h e d r a l s t e r e o c h e m i s t r y . ί M o r e r e c e n t l y ,
the a b s o l u t e configuration of o n e of the opti­
3 +
cal i s o m e r s of [ C o ( e n ) ] w a s d e t e r m i n e d (see
3
P a n e l on p . 1125).
A n o t h e r N - d o n o r ligand, w h i c h f o r m s e x t r e ­
m e l y stable c o m p l e x e s , is t h e Ν θ 2 ~ ion: its
b e s t - k n o w n c o m p l e x is the o r a n g e " s o d i u m
3
tions of w h i c h w e r e u s e d for the q u a n t i t a t i v e
+
precipitation of K as K [ C O ( N 0 2 ) O ] in classical
3
a n a l y s i s . T r e a t m e n t of this w i t h fluorine yields
£ S o d e e p - s e a t e d at that t i m e w a s the c o n v i c t i o n that o p t i c a l
a c t i v i t y c o u l d arise o n l y f r o m c a r b o n a t o m s that it w a s a r g u e d
that the e t h y l e n e d i a m i n e m u s t b e r e s p o n s i b l e , e v e n t h o u g h it
is i t s e l f o p t i c a l l y i n a c t i v e . T h e o p p o s i t i o n w a s o n l y finally
a s s u a g e d b y W e r n e r ' s s u b s e q u e n t r e s o l u t i o n o f an e n t i r e l y
i n o r g a n i c material ( p . 9 1 5 ) .
1124 Cobalt, Rhodium and Iridium Ch. 26

E l e c t r o n T r a n s f e r ( R e d o x ) R e a c t i o n s

t w o mechanisms exist for the transfer of charge from one species to another:
1. Outer-sphere. Here, electron transfer from one reactant to the other is effected without changing &e coordination
sphere of either. This is likely to be the case If both reactants ate coordinatively saturated and can safely be assumed to
he so if the rate of the redox process is faster than the rates observed for substitution (ligand transfer) reactions of tfce
species in question. A*good example is the reaction,

[Fe^CN^] " + 4 llf"a ?~

6 [Fe (CN) J ~ 4-
m 6 3 U^Ckf*

The observed rate law for this type of reaction is usually first order in each reactant. Extensive theoretical treatments
have been performed, most notably by R. A. Marcus and N. S. Hush, details of which can be found in more specialized
sources* * 14

2. Inner-sphere. Here, the two reactants first form a bridged complex (precursory, intramolecular electron transfer
then yields the successor which in turn dissociates to give the products, The first demonstration of this was provided by
H. Taube. He examined the oxidation of [Cr(H20kJ * by fCoCKNHs&J * and postulated that it occurs as follows:
2 2

[Cr«<H 0) ] * + ta>H*a(NH ) ]
2 6 2 3 5 2+ r(H 0) Or -C^Co (NH3)5l
2 5 lI m 4+

precursor
electron
transfer

[Cr«i(H 0) Cl) * + tCo»(NH )5H 01

2 5 2 3 2 2+ ^ J & 2 L [(Μ 0)^ 2 - Cl~Co (NH3) ]
n 5 4t

successor

ί^»(Η 0) ] %5ΝΗ4*
2 6 2

The superb elegance of this demonstration lies in the choice of reactants which permits no alternative mechanism. Cr (d ) 11 4

and Co (d ) species are known to be substitutionary labile whereas Cr (d ) and Co (low-spin d ) are substitutjonally
11 7 01 3 111 6

inert. Only if electron transfer is preceded by the formation of a bridged intermediate can the inert œbaît reactant
be persuaded to release a Cl~ ligand and so allow the quantitative formation of the (then inert) chromium product
Corroboration that electron transfer does not occur by an outer-sphere mechanism followed by loss of € T from
chromium is provided by the fact that, if C F is added to the solution, none of it finds its way into the c h K H n i u m
3 6

product. V
Demonstration of ligand transfer is crucial to the proof that this particular reaction proceeds via an irmer-spheie
mechanism, and ligand transfer is indeed a usual feature of inner-sphere redox reactions, but it is not an essential feature
of all such reactions.
The observed rate l a w for inner-sphere, as for outer-sphere, reactions is commonly first order in each reactant but this
does not indicate which step is rate-determining. Again, details should be obtained from more extensive accounts/ * ;| 14

For their work in thisfield,Taube and Marcus w e r e awarded Nobel Prizes f o r Chemistry in 1983 and 1992 respectively. -

[Co(CN)6] h a s already been mentioned a n d

K [ C o F 6 ] , w h o s e a n i o n is n o t a b l e n o t o n l y a s
3

is e x t r e m e l y stable, b e i n g inert t o alkalis and, like

the o n l y h e x a h a l o g e n o c o m p l e x of cobalt(III) b u t
a l s o for b e i n g h i g h - s p i n a n d h e n c e p a r a m a g n e t i c [ F e ( C N ) 6 ] " , w h i c h l i k e w i s e i n v o l v e s the t\
4 g con-
w i t h a m a g n e t i c m o m e n t at r o o m t e m p e r a t u r e of figuration, it is r e p o r t e d l y n o n t o x i c .
n e a r l y 5.8 B M . C o m p l e x e s of cobalt(III) w i t h O - d o n o r l i g a n d s
are g e n e r a l l y less stable t h a n t h o s e w i t h -donors
R . G . W I L K I N S , Kinetics
1 4 and Mechanism of Reactions of
a l t h o u g h the d a r k - g r e e n [ C o ( a c a c ) ] a n d M [ C o - 3 3

Transition Metal Complexes, 2nd edn., V C H , Weinhein, (C2U4) ] c o m p l e x e s , f o r m e d f r o m t h e c h e l a t i n g

3

1991, 4 6 5 pp. T . J. M E Y E R and H. T A U B E , Chap. 9 in

l i g a n d s a c e t y l a c e t o n a t e a n d o x a l a t e , a r e stable.
Comprehensive Coordination Chemistry, Vol. 1 , p p . 3 3 1 - 8 4 ,
Pergamon Press, Oxford, 1 9 8 7 . O t h e r c a r b o x y l a t o c o m p l e x e s s u c h a s t h o s e of
§26.3.3 Complexes 1125

Determination of Absolute Configuration |

Because they rotate the plane of polarized light in opposite directions (p. 919) it is a relatively simple matter to distinguish ;
an optical isomer from its mirror image. But to establish their absolute configurations is a problem which for long
defeated the ingenuity of chemists. Normal X-ray diffraction techniques do not distinguish between Chem, but J. M. Bijvoet
developed the absorption edge, or anomalous, diffraction technique which does. In this method the wavelength of the
X-rays is chosen so as to correspond to an electronic transition of the central metal atom, and under these circumstances
phase changes are introduced into the diffracted radiation which are different for the two isomers. An understanding of
the phenomenon not only allows the isomers to be distinguished but also their configurations to be identified. Once the
absolute configuration of one complex has been determined in this way, it can then be used as a standard to determine
the absolute configuration of other, similar, complexes by the relatively simpler method of comparing their optica! rotary
dispersion (ORD) and circular dichroism (CD) curves/ * 15

Normal measurements of optical activity are concerned with the ability of the optically active substance to rotate the
plane of polarization of plane polarized light, its specific optical rotatory power (a ) being given by
m

«m = —τ radnrkg J

where α is the observed angle of rotation, V is the volume, m is the mass, and / is the path length.
The reason why this phenomenon occurs is that plane polarized light can be considered to be made up of left- and of
right-circularly polarized components, and the nature of an optically active substance is such that, in passing through it,
one component passes through greater electron density than does the other. As a result, that component is slowed down
relative to the other and the two components emerge somewhat out-of-phase, i.e. the plane of polarization of the light
has been rotated. If the wavelength of the polarized light is varied, and a then plotted against wavelength, the result is
m

known as an optical rotary dispersion curve. For those wavelengths at which the substance is transparent, a is virtually
m

constant, which is to say the ORD curve is flat. But what happens when the wavelength of the light is such mat it is
. absorbed by aie substance in question?
In absorbing light the molecules of a substance undergo electronic excitations which involve displacement of electron
< charge. Because of their differing routes through the molecules, the two circularly polarized components of the light
produce these excitations to different extents and are consequently absorbed to different extents. The difference in extinction
coefficients, <?ift-bright, can be measured and is known as the circular dichroism. If the CD is plotted against wavelength
e

it is therefore zero at wavelengths where there is no absorption but passes through a maximum, or a minimum, where
absorption occurs. Accompanying these changes in CD it is found that the ORD curve is like a first derivative, passing
through zero at the absorption maximum (Fig. A). Such a change in sign of a highlights the importance of quoting the
m

wavelength of the light used when classifying optical isomers as (-f ) or ( - ) , since the classification could be reversed by
simply using light of a different wavelength.^

Figure A Diagrammatic representation of the Cotton effect (actually "positive" Cotton effect. The "negative" effect
occurs when the CD curve shows a minimum and the ORD curve is the reverse of the above).
Panel continues

^The situation is perhaps not quite so bad as is implied here, since single measurements of a are usually made at
m

the sodium D line, 589.6 nm. Nevertheless, it is clearly better to state the wavelength than to assume that this will be
understood.

l 5 R . D . G I L L A R D , Prog. Inorg. Chem. 7, 2 1 5 - 7 6 (1966).

1126 Cobalt, Rhodium and Iridium Ch. 26

The behaviours of CD and ORD curves in the vicinity of an absorption band are collectively known as the Cotton
effect alter the French physicist A. Cotton who discovered mem in 1895. Tlieir importance in the present context is that
molecules with the same absolute configuration will exhibit the same Cotton effect for the same d-d absorption and, if
the configuration of one compound is known, that of closely similar ones can be established by comparison.
Hie optical isomer of [Co(en>3l referred to in the main text is the (4~>NaD isomer, which has a left-handed (laevo)
3+

screw axis as shown in fig. Ba, and according to the convention recommended by IUPAC is given the symbol A. This
is in contrast to its mirror image (Fig. Bb) which has a right-handed (dextro) screw axis and is given the symbol Δ.

(a) Λ configuration (b) Δ configuration

Figure Β The absolute configuration of the optical isomers of a metal tris-chelates complex such as
[Co(en>3) . (a) A configuration and (b) Δ configuration.
3+

the a c e t a t e a r e , h o w e v e r , less stable b u t a r e of a catalyst, t o isolate a b r o w n i n t e r m e d i ­

i n v o l v e d in t h e catalysis of a n u m b e r of o x i d a t i o n ate, [ ( N H ) C o - 0 - C o ( N H ) ] + . T h i s is m o d ­
3 5 2 3 5 4

reactions by C o 1 1 carboxylates. erately stable in c o n e a q u e o u s a m m o n i a a n d in

A n o t i c e a b l e difference b e t w e e n t h e c h e m i s ­ t h e solid, b u t d e c o m p o s e s r e a d i l y in acid solu­
tries of complexes of chromium(III) and tions t o C o a n d O2, w h i l e o x i d i z i n g a g e n t s
1 1

cobalt(III) is t h e s m a l l e r susceptibility of t h e s u c h as (S2O8)2" c o n v e r t it t o t h e g r e e n , p a r a ­

latter t o h y d r o l y s i s , t h o u g h l i m i t e d h y d r o l y s i s , magnetic [ ( Ν Η ) € ο - θ 2 - € ο ( Ν Η ) ] ( μ ο ο ~
3 5 3 5 5 + 3

leading to polynuclear cobaltammines with 1.7 B M ) . T h e f o r m u l a t i o n of t h e b r o w n c o m ­

bridging O H ~ g r o u p s , is well k n o w n . Other pound poses no problems. T h e 2 cobalt atoms
commonly occurring bridging groups are N H 2 ~ , a r e in t h e + 3 o x i d a t i o n state a n d a r e j o i n e d b y
NH 2 _ a n d N Û 2 , a n d singly, d o u b l y a n d triply
-
a p e r o x o g r o u p , 02 ~, all of w h i c h a c c o r d s w i t h
2

b r i d g e d s p e c i e s a r e k n o w n s u c h as t h e o b s e r v e d d i a m a g n e t i s m ; m o r e o v e r , t h e stere­
o c h e m i s t r y of t h e c e n t r a l C o - 0 - 0 - C o g r o u p
the b r i g h t - b l u e [ ( N H ) C o - N H 2 - C o ( N H ) ]
3 5 3 5 5 + , (Fig. 2 6 . 2 a ) is a k i n t o that of H 2 0 2 ( p . 6 3 4 ) . T h e
g r e e n c o m p o u n d is less s t r a i g h t f o r w a r d . W e r n e r
ΌΗ^
garnet-red [(NH ) ]Co^
3 4 .Co(NH ) f ,
3 4 +
t h o u g h t that it t o o i n v o l v e d a p e r o x o g r o u p b u t
OH in this i n s t a n c e b r i d g i n g C o and C o
1 1 1 atoms. I V

ΝΗ ! χ

and red [(NH ) Co-OH-Co(NH3)3]

3 3 3 +

OH

B u t p r o b a b l y t h e m o s t interesting of t h e p o l y n u ­
clear complexes are those containing - O - O -
b r i d g e s ( s e e also p . 6 1 6 ) .
In t h e p r e p a r a t i o n of cobalt(III) h e x a a m m i n e F i g u r e 26.2 0 bridges in dinuclear cobalt com­
2

salts b y t h e aerial' o x i d a t i o n of cobalt(II) in plexes: (a) peroxo ( 0 ~ ) bridge, and 2 2

a q u e o u s a m m o n i a it is p o s s i b l e , in t h e a b s e n c e (b) superoxo ( O 2 ) bridge. -

§26.3.3 Complexes 1127

Table 26.5 Spectra of octahedral low-spin complexes of cobalt(III)

1 1
Complex Colour vi/cm _ 1
v /cm
2
1
lODq/cm' 5/cirT

[Co(H 0) ] 2 6
3 +
Blue 16600 24 800 18 200 670
[Co(NH ) ] 3 6
3 +
Golden-brown 21000 29500 22900 620
[Co(C 0 ) ] - 2 4 3
3
Dark green 16600 23 800 18000 540
[Co(en) ] 3
3+
Yellow 21400 29500 23 200 590
3
[Co(CN) ] " 6 Yellow 32400 39000 33 500 460

T h i s c o u l d a c c o u n t for t h e p a r a m a g n e t i s m , b u t C o m p l e x e s of rhodium(III) are usually derived,

e s r e v i d e n c e s h o w s that t h e 2 c o b a l t a t o m s a r e directly or indirectly, from RI1CI3.3H2O a n d those
actually equivalent, a n d X-ray evidence shows of i r i d i u m ( I I I ) f r o m ( Ν Η ) [ Ι ι € 1 ] . A l l t h e c o m ­
4 3 6

m 111
the central C o - O - O - C o group to be planar pounds of R h and Ir are diamagnetic and low-
w i t h a n 0 - 0 d i s t a n c e of 131 p m , w h i c h is v e r y spin, t h e v a s t m a j o r i t y of t h e m b e i n g o c t a h e d r a l
c l o s e t o t h e 128 p m of t h e s u p e r o x i d e , 0 2 ~ , w i t h t h e t\ g configuration. Their electronic spec­
ion. A m o r e satisfactory f o r m u l a t i o n therefore tra c a n b e i n t e r p r e t e d in t h e s a m e w a y a s t h e
1 1 1
is that o f 2 C o 1 1 1
atoms joined by a superoxide s p e c t r a of C o complexes, though the second
m

b r i d g e . M o l e c u l a r orbital t h e o r y predicts that d - d b a n d , e s p e c i a l l y i n t h e c a s e o f I r , is fre­

t h e u n p a i r e d e l e c t r o n is situated in a π orbital quently obscured b y charge-transfer absorption.
e x t e n d i n g o v e r all 4 a t o m s . If this is t h e c a s e , T h e d - d a b s o r p t i o n s at t h e b l u e e n d of t h e v i s ­
t h e n t h e π orbital is e v i d e n t l y c o n c e n t r a t e d v e r y ible r e g i o n a r e r e s p o n s i b l e for t h e y e l l o w t o r e d
1 1 1

largely o n t h e b r i d g i n g o x y g e n a t o m s . colours which characterize R h complexes.

If [(NH ) Co-0 -Co(NH ) ] 4 +

is treated S i m i l a r i t y w i t h c o b a l t is a l s o a p p a r e n t i n t h e
3 5 2 3 5
m 111

with aqueous KOH another brown com­ affinity o f R h and Ir for a m m o n i a a n d a m i n e s .

m

plex, [ ( Ν Η ) 4 € ο ( μ - Ν Η 2 ) ( μ - θ 2 ^ ο ( Ν Η ) 4 ] 3 +
is T h e kinetic inertness of the a m m i n e s of R h
3 3

h a s l e d t o t h e u s e o f s e v e r a l o f t h e m in s t u d i e s
o b t a i n e d a n d , a g a i n , a 1-electron o x i d a t i o n y i e l d s
of t h e trans effect ( p . 1 1 6 3 ) in o c t a h e d r a l c o m ­
a green superoxo species, [ ( Ν Η ) 4 θ ) ( μ - Ν Η 2 ) - 3
m
4 + plexes, while the a m m i n e s of I r are so stable
^-0 )Co(NH ) ]
2 3 4 T h e sulfate o f this lat­
as t o w i t h s t a n d b o i l i n g i n a q u e o u s alkali. S t a ­
ter is a c t u a l l y o n e c o m p o n e n t of V o r t m a n n ' s 3 _
ble complexes such as [ M ( C 2 0 4 > ] , [ M ( a c a c ) ] 3 3
sulfate — t h e o t h e r is t h e r e d [ ( Ν Η ) 0 ) ( μ - Ν Η ) - 3 4 2
3
and [ M ( C N ) 6 ] ~ a r e f o r m e d b y all t h r e e m e t ­
^-OH)Co(NH ) ](S0 ) . 3 4 4 2 They are obtained
als. F o r c e c o n s t a n t s o b t a i n e d f r o m t h e infrared
by aerial oxidation of a m m o n i a c a l solutions
spectra of the h e x a c y a n o complexes indicate
of c o b a l t ( I I ) nitrate f o l l o w e d b y n e u t r a l i z a t i o n
that t h e M - C b o n d s t r e n g t h i n c r e a s e s i n t h e
with H S 0 . 2 4
o r d e r C o < R h < Ir. L i k e c o b a l t , r h o d i u m t o o
Apart from the above green superoxo-bridged
forms bridged superoxides such as the blue, para­
complexes and the blue fluoro complexes, 5 +
magnetic, [Cl(py) Rh-0 -Rh(py) Cl]
4 2 4 pro­
3
[CoF ] " and [ C o F ( H 0 ) ] , octahedral com­
6 3 2 3
d u c e d b y a e r i a l o x i d a t i o n of a q u e o u s e t h a n o l i c
plexes of cobalt(III) (being low-spin) are diamag­ ( 1 7 )
s o l u t i o n s of R h C l 3 and pyridine. I n fact it
n e t i c . T h e i r m a g n e t i c p r o p e r t i e s a r e t h e r e f o r e of
s e e m s likely that m a n y o f t h e s p e c i e s p r o d u c e d b y
little i n t e r e s t b u t , s o m e w h a t u n u s u a l l y for l o w - o x i d a t i o n of a q u e o u s s o l u t i o n s of R h m
and pre­
s p i n c o m p o u n d s , their e l e c t r o n i c s p e c t r a have s u m e d t o c o n t a i n t h e m e t a l in h i g h e r o x i d a t i o n
( 1 6 )
received a good deal of a t t e n t i o n (see Panel states, a r e a c t u a l l y s u p e r o x i d e s of R h . m ( 1 8 )

o n p . 1 1 2 8 ) . D a t a for a r e p r e s e n t a t i v e s a m p l e o f
c o m p l e x e s a r e g i v e n in T a b l e 2 6 . 5
1 7
N . S. A . E D W A R D S , I. J. E L L I S O N , R. D . G I L L A R D and
B . M I L E , Polyhedron 12, 3 7 1 - 4 (1993).
1
A . B . P . L E V E R , Inorganic Electronic Spectroscopy, 2nd 1 8
1 . J. E L L I S O N and R. D . G I L L A R D , J. Chem. Soc, Chem.
edn., pp. 4 7 3 - 7 , Elsevier, Amsterdam, 1984. Commun., 8 5 1 - 3 (1992).
1128 Cobalt, Rhodium and Iridium Ch. 26

^^^^^H^^^K'lM^^ A» visible region

• -

: f%m Λ Simplified Energy Level diagram for d tons showing possible spin-allowed transitions in
6

These t r a i ^ promotion ^ with the prorrK)ted electron mamtaimng ifβ

unaltered. 13» ortEal multiplicity of the φ ? * configuration is 6 and so corresponds to two orbital triplet terms Τι éd' ι $

t f ^ J M * * » other, hand, the promoted electron changes its spin, the orbital mMpEcity is again 6 but the two F terms
m&mw ^ t r i p l e t s , *Tt$ and T%& h wwbtmâ attributable Id ûm spm-forbidiiten r ^ V U ^ transition is indeed
% 3

£ Data for some typical coiriplexes are given in Table 26.5. The assignments are made, producmg values of the inter-
electronic r e g i o n |>ar«me^r B m well as of me crystal-field splitting. lQDç.
The colours of car and mm$ isomers of complexes {C0L4X2Î or [€qÇL~L%X2] frequently differ and, aJWKwgh simple
observation of colour will not alone suffice to establish a ds or trans geofoetry, an examination of the electronic spectra
does have diagnostic value. Calculations of the effect of low-symmetry components in me crystal field show that the tau»
isomer will split the excited terms appreciably more than the a s , and the effect is most marked for Tt»» the lowest of Ε ξ
1

excited terms. Ha practice, if L-L and X are sufficiently far apart in the spectrochemicai series (e.g. I h L « en and X * r
which has been thorou^ly examined), the band splits completely, giving rise to three separate bands for the frémi
complex whereas the cis merely shows slight asymmetry in the lower energy band. Furthermore, because (tike tetrahedral
complexes) a cis isomer lacks a centre of symmetry, its spectrum is more intense than that of the centrosymmetric tram j
isomer. . ; J;';
It is relevant to note at this point mat, because the metal ions are isoelectrome, the spectra of low-spin Fe complexes11

mi^bt be expected to be similar to those of low-spin Co* . However, Fe requires a much stronger crystal field to
11 11

effect spin-pairing and the ligands which provide such a field also give rise to low-energy charge-transfer bands w h u
mimm^^^.db^^M d~4 ba*d& N e ^ M e s s , the spectrum of the pate-yellow fpe(QQ$] "~ shows a shoulép:jg
4

SÎÙÙÙcmr on the side of a charge transfer absorption and this is attributed to the Ti +- Ai
1 l g transition.
l g
§26.3.3 Complexes 1129

D e s p i t e t h e a b o v e similarities, m a n y differ- interesting feature o f their chemistry is the ease

e n c e s b e t w e e n the m e m b e r s o f this triad a r e a l s o with w h i c h they afford hydride and carbonyl
to b e n o t e d . R e d u c t i o n o f a trivalent c o m p o u n d , derivatives. For instance, the colourless, air-
which yields a divalent c o m p o u n d in t h e case stable [ R h H ( N H 3 ) 5 ] S 0 4 is produced by the action
of cobalt, r a r e l y d o e s s o f o r t h e h e a v i e r e l e - of Z n p o w d e r o n ammoniacal RΞ1CI3 in the
ments where the metal, univalent compounds, presence o f ( N F U ^ S C U :
m
or M hydrido complexes are the more usual Zn
p r o d u c t s . R h o d i u m f o r m s t h e q u i t e stable, y e l - [RhCl(NH ) ]Cl2 ^ 3 5 [RhH(NH ) ]S0
3 5 4
3+
l o w [Rh(H2Û)6] i o n w h e n h y d r o u s Rh2U3 i s
d i s s o l v e d in m i n e r a l acid, a n d it o c c u r s in t h e Ternary hydrides o f R h and Ir containing
3

solid state in salts s u c h a s t h e p e r c h l o r a t e , sulfate
3+
a n d a l u m s . [ I r ( H 2 0 ) 6 ] is less r e a d i l y o b t a i n e d
b u t h a s b e e n s h o w n t o o c c u r in s o l u t i o n s o f I r
in c o n e HCIO4.
T h e r e is a l s o c l e a r e v i d e n c e o f a c h a n g e
from p r e d o m i n a n t l y c l a s s - a t o c l a s s - b m e t a l
charactristics ( p . 9 0 9 ) in p a s s i n g d o w n this g r o u p .
W h e r e a s cobalt(III) forms few complexes with
the h e a v i e r d o n o r a t o m s o f G r o u p s 15 a n d
16, r h o d i u m ( I I I ) , a n d m o r e e s p e c i a l l y i r i d i u m
(III), c o o r d i n a t e r e a d i l y w i t h As- a n d S-
d o n o r l i g a n d s . C o m p o u n d s w i t h Se- a n d e v e n
( 1 9 )
Te- a r e also k n o w n . T h u s infrared, X - r a y
1 4
and N n m r studies s h o w that, in c o m p l e x e s
+
s u c h a s [Co(NH3)4(NCS)2] , t h e N C S " acts a s
an N - d o n o r ligand, w h e r e a s in [ M ( S C N ) ]
( M = R h , I r ) it is a n 5 - d o n o r . L i k e w i s e in t h e
the octahedral [ M H O ] " anions have been
(20)
prepared b y the reaction o f LiH and the metal
111 under a high pressure o f H2. It is h o w e v e r
unusual for hydrides o f metals in such a high
formal oxidation state as 4 - 3 to b e stable in
the absence o f 7r-acceptor ligands and, indeed,
in the presence o f π-acceptor ligands such as
tertiary phosphines and arsines, the stability
of rhodium(III) hydrides is enhanced. Thus
H3PO2 reduces [ R h C l L ] to either [ R h H C l L ]
3 3 2 3
or [RI1H2CIL3], depending o n L; and the
I
action o f H o n [ R h ( P P h ) X ] ( X = CI, Br,
2 3 3
I) yields [ R h H ( P P h ) X ] w h i c h i s , formally
2 3 3
at least, an oxidation b y molecular hydrogen.
H o w e v e r , it is iridium(III) that forms more
3 _
hydrido-phosphine and hydrido-arsine c o m p l e x e s
6
than any other platinum metal. U s i n g NaBH4,
L1AIH4, EtOH or e v e n S n C l + H + to provide 2

h e x a h a l o g e n o c o m p l e x a n i o n s , [ΜΧβΫ~, cobalt
forms o n l y that w i t h fluoride, w h e r e a s r h o d i u m
forms t h e m w i t h all the h a l i d e s e x c e p t i o d i d e , a n d
i r i d i u m f o r m s t h e m w i t h all e x c e p t fluoride.
B e s i d e s the t h i o c y a n a t e s , j u s t m e n t i o n e d , o t h e r
5 - d o n o r c o m p l e x e s w h i c h a r e o f interest a r e
the hydride ligand, c o m p l e x e s o f the type
[ M H „ L 3 X 3 _ , J can b e formed for very many o f
the permutations w h i c h are possible from L =
trialkyl or triaryl phosphine or arsine; X = CI,
Br or I. Many polynuclear hydride c o m p l e x e s are
also k n o w n / 2 1 )

the dialkyl sulfides, [MCl3(SR2)3], p r o d u c e d b y

the action o f SR2 o n e t h a n o l i c RI1CI3 o r o n
3 -
[ I r C l o ] . P h o s p h o r u s a n d a r s e n i c c o m p o u n d s are Oxidation state II ( d ) 7

o b t a i n e d in similar fashion, a n d t h e b e s t k n o w n
There is a very marked contrast in this oxidation
are t h e y e l l o w t o o r a n g e c o m p l e x e s , [ML3X3],
state b e t w e e n cobalt on the one hand, and the t w o
( M = R h , Ir; X = C l , Br, I; L = trialkyl o r triaryl
heavier members o f the group o n the other. For
phosphine o r arsine). These c o m p o u n d s m a y
cobalt it is one o f the t w o most stable oxidation
exist a s either mer o r fac i s o m e r s , a n d t h e s e
states, whereas for the others it is o f only minor
are n o r m a l l y d i s t i n g u i s h e d b y their p r o t o n n m r
importance.
s p e c t r a ( a distinction p r e v i o u s l y m a d e b y t h e
measurement of dipole moments). A n especially
2 0
W . B R O N G E R , M . G E H L E N a n d G . A U F F E R M A N N , Ζ. anorg.
allg. Chem. 6 2 0 , 1 9 8 3 - 5 (1994).
1 9
A . Z . AL-RUBAIE, Y . N . AL-OBAIDI and L . Z . YOUSIF, 2 1
T . M . G . C A R N E I R O , D . M A T T and P . B R A U N S T E I N , Coord.
Polyhedron 9 , 1 1 4 1 - 6 (1990). Chem. Revs. 9 6 , 4 9 - 8 8 (1989).
1130 Cobalt, Rhodium and Iridium Ch. 26

M a n y early r e p o r t s of R h a n d I r c o m p l e x e s 11 11 n o solid salt of this h a s b e e n isolated. W h y

11

h a v e n o t b e e n verified a n d i n s o m e c a s e s m a y no comparable Ir c a r b o x y l a t e s , a n d very f e w

have involved M hydrides. Monomeric com­ I H o t h e r d i m e r i c s p e c i e s stabilized b y m e t a l - m e t a l
p o u n d s r e q u i r e stabilization b y l i g a n d s s u c h b o n d i n g , h a v e y e t b e e n p r e p a r e d is n o t clear.
1 1
as p h o s p h i n e s o r CeC\s~. T h u s , t h e action B y contrast, C o c a r b o x y l a t e s s u c h as t h e r e d
of L i C C l o n [ L M - C 1 - M L ] , w h e r e L =
6 5 2 2 2
acetate, C o ( 0 C M e ) . 4 H 0 , are monomeric and
2 2 2

2 [ P ( O P h ) ] , cyclooctene or cycloocta-l,5-diene,
3
in s o m e c a s e s t h e c a r b o x y l a t e l i g a n d s a r e u n i d e n -
affords trans s q u a r e p l a n a r p r o d u c t s of t h e t y p e tate. T h e a c e t a t e is e m p l o y e d in t h e p r o d u c t i o n of
I 1
[ M ( r 7 - C C l ) 2 ( L ) ] " , o x i d a t i o n o f w h i c h yield
6 5 2
c a t a l y s t s u s e d in certain o r g a n i c o x i d a t i o n s , a n d
monomeric paramagnetic compounds such as also a s a d r y i n g a g e n t in o i l - b a s e d p a i n t s a n d
I I 1
[ M ( ? 7 - C C l 5 ) ( L ) ] a n d , in t h e c a s e of i r i d i u m ,
6 2 2
v a r n i s h e s . C o b a l t ( I I ) g i v e s rise t o s i m p l e salts
square planar [ I r ^ ^ - C o C l s M i s o l a t e d a s its 2 -
w i t h all t h e c o m m o n a n i o n s a n d they a r e r e a d ­
(NBU4)4" s a l t . R h o d i u m ( I I ) is s o m e w h a t m o r e
( 2 2 )
ily o b t a i n e d a s h y d r a t e s from a q u e o u s solutions.
c o m m o n t h a n i r i d i u m ( I I ) . P a r a m a g n e t i c , trans T h e parent hydroxide, C o ( O H ) , can be precipi­ 2

square planar phosphines [ R h C l L ] and the 2 2

tated f r o m t h e a q u e o u s s o l u t i o n s b y t h e addition
alkyl ( R h R ( t h t ) ] , ( R = 2 , 4 , 6 - P r C H ; tht =
2 2 3 6 2 of alkali a n d is s o m e w h a t a m p h o t e r i c , n o t only
tetrahydrothiophene) have been characterized. ( 2 3 )
d i s s o l v i n g in acid b u t also r e d i s s o l v i n g in e x c e s s
Also, depending o n temperature and relative con­ of c o n e alkali, in w h i c h c a s e it g i v e s a d e e p -
c e n t r a t i o n s , t h e r e a c t i o n of R h ( N O ) C l ( P P h ) 2 3 2 b l u e solution c o n t a i n i n g [ C o ( O H ) ] ~ ions. It is 4
2

a n d N a ( S C N R ) in b e n z e n e y i e l d s e i t h e r
2 2 o b t a i n a b l e in b o t h b l u e a n d p i n k varieties: t h e
R h ( S C N R ) or R h ( S C N R ) ( P P h ) , character­
2 2 2 2 2 3 f o r m e r is p r e c i p i t a t e d b y s l o w a d d i t i o n of alkali
ized b y s p e c t r o s c o p i c m e t h o d s a s s q u a r e p l a n a r at 0 ° C , b u t it is u n s t a b l e a n d , in t h e a b s e n c e of
(24)
and square pyramidal r e s p e c t i v e l y . air, b e c o m e s p i n k o n w a r m i n g (cf. p . 1131).
Rhodium(II), however, is m o s t familiar C o m p l e x e s of c o b a l t ( I I ) are less n u m e r o u s than
in a series of g r e e n d i m e r i c diamagnetic t h o s e o f cobalt(III) but, l a c k i n g a n y configuration
( 2 5 )
compounds. If h y d r o u s R h 0 , o r b e t t e r 2 3 comparable in stability w i t h t h e t\ g of C o 1 1 1
,
still R h C l . 3 H 0 a n d s o d i u m c a r b o x y l a t e , is
3 2 they s h o w a g r e a t e r diversity o f t y p e s a n d a r e
refluxed with t h e a p p r o p r i a t e acid a n d a l c o h o l , m o r e labile. T h e r e d o x p r o p e r t i e s h a v e a l r e a d y
g r e e n o r b l u e s o l v a t e d [ R h ( 0 C R ) ] is f o r m e d . 2 2 2 b e e n referred t o a n d t h e possibility of o x i d a t i o n
C o m p o u n d s of this t y p e a r e g e n e r a l l y air-stable must always be considered when preparing
a n d h a v e t h e s a m e b r i d g e d structure as t h e Co 1 1
complexes. However, providing solutions
11 1 1 11
c a r b o x y l a t e s o f C r , M o a n d C u ; in t h e c a s e are n o t a l k a l i n e a n d t h e l i g a n d s n o t t o o h i g h
of t h e a c e t a t e this i n v o l v e s a R h - R h d i s t a n c e of in t h e s p e c t r o c h e m i c a l series, a large number
2 3 9 p m w h i c h is c o n s i s t e n t with a R h - R h b o n d . of c o m p l e x e s c a n b e isolated w i t h o u t special
If r h o d i u m a c e t a t e is treated w i t h a strong acid p r e c a u t i o n s . T h e m o s t c o m m o n t y p e is h i g h - s p i n
s u c h a s HBF4, w h o s e a n i o n h a s little t e n d e n c y t o octahedral, though spin-pairing can b e achieved
c o o r d i n a t e , g r e e n solutions a p p a r e n t l y c o n t a i n i n g b y l i g a n d s s u c h a s C N ~ ( p . 1 1 3 3 ) w h i c h also
4 +
the diamagnetic R h ion are obtained but 2 f a v o u r t h e h i g h e r o x i d a t i o n state. Appropriate
c h o i c e of l i g a n d s c a n h o w e v e r lead t o h i g h - s p i n -
2 2
M . P. G A R C I A , M . V. JIMENEZ, L. A . O R O and F. J . l o w - s p i n e q u i l i b r i a a s in [ C o ( t e r p y ) ] X . t t H 0 2 2 2

L A H O Z , Organometallics 12, 4 6 6 0 - 3 ( 1 9 9 3 ) .
a n d s o m e 5 - a n d 6 - c o o r d i n a t e d c o m p l e x e s of
2 3
R . S. HAY-MOTHERWELL, S . U . KOSCHMIEDER, G . WILK­ ( 2 6 )
Schiff b a s e s a n d p y r i d i n e s .
I N S O N , B . H U S S A I N - B A T E S a n d M . B . H U R S T H O U S E , J. Chem.
Soc, Dalton Trans., 2 8 2 1 - 3 0 (1991). Many of the hydrated salts and their
2 4
Κ . K . P A N D E Y , D . T . N E H E T E and R . B . S H A R M A , Polyhe­ a q u e o u s solutions c o n t a i n t h e o c t a h e d r a l , p i n k
dron 9, 2 0 1 3 - 1 8 ( 1 9 9 0 ) .
2 5
F. A . C O T T O N and R . A. WALTON, Multiple Bonds
2 6

Between Metal Atoms, Clarendon Press, Oxford, 1 9 9 3 , P . THUERY and J. ZARAMBOWITCH, Inorg. Chem. 25,

7 8 7 pp. 2 0 0 1 - 8 (1986).
§26.3.3 Complexes 1131

Table 26.6 CFSE values^ for high-spin complexes

of d° to d ions 10

No. of d electrons 0 1 2 3 4 5 6 7 8 9 10
2 4 6 3 2 4 6 3
CFSE(oct)/(A ) 0 0 5 5 5 5
0 5 5 5 5
0
3 6 4 2 3 6 4 2
CFSE(tet)/(A ) t 0 5 5 5 5
0 5 5 5 5
0

Ξ T he C r y s t a l F i e l d S t a b i l i z a t i o n E n e r g y ( C F S E ) i s t h e
a d d i t i o n a l stability w h i c h a c c r u e s t o a n i o n i n a c o m p l e x , a s
c o m p a r e d t o t h e free i o n , b e c a u s e i t s d-orbitals are split. In
an o c t a h e d r a l c o m p l e x a ti e l e c t r o n i n c r e a s e s t h e stability
g

b y 2 / 5 Δ a n d a n e e l e c t r o n d e c r e a s e s it b y 3 / 5 Δ . In a
0 g 0

F i g u r e 26.3 The tetrameric structure of [Co(acac)2 k ]. tetrahedral c o m p l e x t h e orbital splitting i s r e v e r s e d a n d a n e

e l e c t r o n therefore i n c r e a s e s t h e stability b y 3 / 5 A w h e r e a s a t

t2 e l e c t r o n d e c r e a s e s it b y 2 / 5 A . t

[Co(H20)6] 2 + ion, and bidentate N - d o n o r ligands

such as en, bipy and phen form octahedral
a n o c t a h e d r a l s t e r e o c h e m i s t r y . T h u s , in a q u e o u s
cationic complexes [Co(L-L)3] , 3 + which are
solutions containing [Co((H20)6] 2 + there are
much more stable to oxidation than is t h e
also present in equilibrium, small amounts of
hexaammine [Co(NH3)6] 2 + . Acac yields the
tetrahedral [Co(H20)4] , 2 + a n d i n acetic acid
orange [Co(acac)2(H20)2] which has the trans
the tetrahedral [Co(02CMe)4] ~ 2 occurs. T h e
octahedral structure and c a n b e dehydrated to
anionic complexes [CoX4] ~ 2 are formed with
[ C o ( a c a c ) ] w h i c h attains o c t a h e d r a l c o o r d i n a t i o n
2
t h e u n i d e n t a t e l i g a n d s , X = C l , B r , I, S C N a n d
by forming the tetrameric species shown in
O H , a n d a w h o l e s e r i e s of c o m p l e x e s , [C0L2X2]
F i g . 2 6 . 3 . T h i s is c o m p a r a b l e w i t h t h e t r i m e r i c
(L = ligand with g r o u p 15 d o n o r atom; X =
[Ni(acac>2]3 (p. 1157), like which it shows
halide, N C S ) , h a s b e e n prepared in which both
evidence of w e a k ferromagnetic interactions at
stereochemistries are found. [CoCl2py2] e x i s t s in
very low temperatures. [Co(edta)(H20)] 2 + is
two isomeric forms: a blue metastable variety
ostensibly analogous to the 7-coordinate M n 1 1 and
w h i c h is m o n o m e r i c a n d t e t r a h e d r a l , a n d a violet,
Fe 11 complexes with the same stoichiometry, but
stable form w h i c h is p o l y m e r i c and achieves
in fact t h e c o b a l t is o n l y 6 - c o o r d i n a t e , 1 o f t h e
octahedral coordination by means of c h l o r i d e
o x y g e n a t o m s o f t h e e d t a b e i n g t o o far a w a y
bridges. Ligand polarizability is a n i m p o r t a n t
f r o m t h e c o b a l t ( 2 7 2 c o m p a r e d t o 2 2 3 p m for
factor determining which stereochemistry is
the other edta donor atoms) to b e considered as adopted, the more polarizable ligands favouring
coordinated. the tetrahedral form s i n c e f e w e r of t h e m a r e
Tetrahedral complexes are also common, required to neutralize the metal's cationic charge.
being formed m o r e readily with cobalt(II) than Thus, if L = p y , r e p l a c e m e n t of C l ~ b y I "
w i t h t h e c a t i o n o f a n y o t h e r truly transitional m a k e s t h e s t a b l e f o r m t e t r a h e d r a l a n d if L =
e l e m e n t ( i . e . e x c l u d i n g Z n ) . T h i s is c o n s i s t e n t
1 1
phosphine or arsine the tetrahedral form is
with the C F S E s of the t w o stereochemistries favoured irrespective of X .
(Table 2 6 . 6 ) . Q u a n t i t a t i v e c o m p a r i s o n s b e t w e e n The most obvious distinction between the
t h e v a l u e s g i v e n for C F S E ( o c t ) a n d C F S E ( t e t ) o c t a h e d r a l a n d t e t r a h e d r a l c o m p o u n d s is that in
a r e n o t p o s s i b l e b e c a u s e of c o u r s e t h e c r y s t a l general the former are pink to violet in colour
field splittings, Δ 0 and A t differ. N o r is t h e w h e r e a s t h e latter a r e b l u e , a s e x e m p l i f i e d b y t h e
C F S E b y a n y m e a n s t h e m o s t i m p o r t a n t factor well-known equilibrium:
in determining the stability of a complex.
Nevertheless, w h e r e other factors are comparable,
[Co(H 0) ] 2 6 2 + + 4C1~ ^ = = ^ [C0CI4] - 2 + 6H 0 2

pink blue
it c a n h a v e a d e c i s i v e effect a n d it is a p p a r e n t
t h a t n o c o n f i g u r a t i o n is m o r e f a v o u r a b l e t h a n d 7 T h i s is n o t a n infallible d i s t i n c t i o n ( a s t h e b l u e b u t
t o t h e a d o p t i o n of a t e t r a h e d r a l a s o p p o s e d t o octahedral C0CI2 d e m o n s t r a t e s ) b u t is a useful
 1132 Cobalt, Rhodium and Iridium Ch. 26

Electronic Spectra and Magnetic Properties of High-spin Octahedral and Tetrahedral

Complexes of Cobalt(II)
Cobait(II) is the only common d ion and because of its stereochemical diversity its spectra have been widely studied,
7

in a cubic field, three spin-allowed transitions are anticipated because of the splitting of me free-ion, ground F term, 4

and the accompanying Ρ term. In the octahedral case the splitting is the same as for the octahedral d ion and the
4 2

spectra can therefore be interpreted in a semi-quantitative manner using the same energy level diagram as was used for
V " (Fig, 22.9, p. 997). In the present case the spectra usually consist of a band in the near infrared, which may be
34

assigned as v\ = T2 (F)<r~ T\ (F),

4 8 and another in the visible, often with a shoulder on the low energy side. Since the
4 g

transition Ai (F)<^T\ (F)

4 $ is essentially a 2-electmn transition from t% e* to f^e* it is expected to be weak, and the
B g

usual assignment is

v (shoulder) =
2 4 A (F)<- Tig(F)
2g 4

v$** T (P)+~ Ti (F)

4 tB 4 g

Indeed, in some cases it is probable that \n is not observed at all, but that the fine structure arises from term splitting due
to spin-orbit coupling or to distortions from regular octahedral symmetry.
. In tetrahedral fields the splitting of the free ion ground term is the reverse of that in octahedral fields so that, for d 7

ions in tetrahedral fiuι& A% (F) lies lowest but three spin-allowed bands are still anticipated.ln fact, the observed spectra
2 %

usually consist of a broad, intense band in the visible region (responsible for the colour and often about 10 times as
intense as in octahedral compounds) with a weaker one in the infrared. The only satisfactory interpretation is to assign
these, respectively, as, vs ~ T\(P)<~- A (F) and v = T\(F)*- A%{F) in which case v\ «s T (F)<r- A (F)
4 4 2 2 4 A should be 4 2 4 2

in the region 3000-5000cm" . Examination of this part of the infrared has sometimes indicated the presence of a band, ;
1

though overlying vibrational bands make interpretation difficult

Table 26.7 gives data for a number of octahedral and tetrahedral complexes, the values of lODq and Β having been |
derived by analysis of the spectra/ * It is clear from these data that the "anomolous" blue colour of octahedral Coda
27

arises because 6 Or ions generate such a weak crystal field that the main band in its spectrum is at an unusually low
energy, extending into the red region (hence giving a blue colour) rather than the green-blue region (which would give a :i

red colour) more commonly observed for octahedral Co compounds. 11 f

Magnetic properties provide a complementary means of distinguishing stereochemistry. The Τ ground term of the
octahedral ion is expected to give rise to a temr^erature-dependent orbital contribution to the magnetic moment whereas
the A ground term of the tetrahedral ion is not. As a matter of fact, in a tetrahedral field the excited T%{F) term is 2 A

"mixed into" the ground Αχ term because of spin-orbit coupling and tetrahedral complexes of C o are expected to have
4 a

magnetic moments given by μ© = Mspin-only^ ~* 4λ/100#), where λ « - 1 7 0 cm" and μ spin-only = 3.87 BM. 1

Thus the magnetic moments of tetrahedral complexes lie in the range 4.4-4.8BM, whereas those of octahedral com- i
plexes are around 4 8 - 5 . 2 BM at room temperature, falling off appreciably as the temperature is reduced.

e m p i r i c a l g u i d e w h o s e reliability is i m p r o v e d b y of their oxygen-carrying properties, discussed

a m o r e careful a n a l y s i s of t h e e l e c t r o n i c s p e c - a l r e a d y in C h a p t e r 14 w h e r e n u m e r o u s r e v i e w s
tra ( 2 7 ) ( s e e P a n e l ) . D a t a for s o m e o c t a h e d r a l a n d o n t h e subject a r e cited. T h e u p t a k e of d i o x y g e n ,
t e t r a h e d r a l c o m p l e x e s a r e g i v e n in T a b l e 2 6 . 7 . which bonds in the bent configuration,
Square planar complexes are also well
a u t h e n t i c a t e d if n o t p a r t i c u l a r l y n u m e r o u s and Ο
/
include [Co(phthalocyanine)] and [Co(CN)4]~ Co — Ο
as well as [Co(salen)] and complexes with
o t h e r Schiff b a s e s . T h e s e a r e i n v a r i a b l y low- is a c c o m p a n i e d b y t h e a t t a c h m e n t of a s o l v e n t
spin w i t h m a g n e t i c m o m e n t s at r o o m t e m p e r a t u r e molecule trans to the O2 and the retention
in t h e r a n g e 2 . 1 - 2 . 9 B M , i n d i c a t i n g 1 u n p a i r e d of t h e s i n g l e u n p a i r e d e l e c t r o n . T h e r e is fairly
e l e c t r o n . T h e y a r e p r i m a r i l y of i n t e r e s t b e c a u s e g e n e r a l a g r e e m e n t , b a s e d o n e s r e v i d e n c e , that
e l e c t r o n transfer f r o m m e t a l to O2 o c c u r s j u s t
p p . 4 8 0 - 5 0 4 o f ref. 16. as in the bridged complexes referred to on
§26.3.3 Complexes 1133

Table 26.7 Electronic spectra of complexes of cobalt(II)

(a) Octahedral
1
ν3 /cm
1
v /cm
2
l
Complex vi/cm 1
(weak) (main) lOD^/cm" 1
B/cm~

[Co(bipy) ] 3
2+
11300 22000 12670 791
[Co(NH ) ] 3 6
2 +
9000 21 100 10200 885
[Co(H 0) ] 2 6
2 +
8100 16000 19400 9200 825
CoCl 2
6600 13 300 17 250 6900 780

(b) Tetrahedral
1
v /cm
3

1
Complex v /cm
2
1
(main) lODtf/cnr 1
B/cm-

[Co(NCS) ] " 4
2
7780 16250 4550 691
[Co(N ) ] - 3 4
2
6750 14900 3920 658
2
[C0CI4] - 5460 14700 3120 710
2
[C0I4] - 4600 13 250 2650 665

p . 1126, producing a situation close to the 3_

[ C o ( C N ) 5 ] , w h i c h is l o w - s p i n w i t h 1 u n p a i r e d
1 1 1
extreme represented by low-spin C o attached e l e c t r o n a n d is s q u a r e p y r a m i d a l . T h e latter c o m ­
to a s u p e r o x i d e ion, 02~. (The opposite extreme, p l e x is isolated f r o m solutions of C o ( C N ) 2 a n d
n
r e p r e s e n t e d b y C o - 0 2 , i m p l i e s that the u n p a i r e d +
K C N as the y e l l o w [ N E t 2 P r 2 ] salt, a n e x t r e m e l y
e l e c t r o n r e s i d e s o n t h e m e t a l w i t h the d i o x y g e n oxygen-sensitive and hygroscopic material. A
b e i n g r e n d e r e d d i a m a g n e t i c b y t h e loss of t h e further difficulty w h i c h h i n d e r e d its isolation is its
d e g e n e r a c y of its π* orbitals w i t h consequent t e n d e n c y to d i m e r i z e to t h e m o r e familiar d e e p -
spin pairing.) H o w e v e r , t h e p r e c i s e e x t e n t of t h e 6
violet, [ ( C N ) C o - C o ( C N ) ] - . T h e a b s e n c e of
5 5

e l e c t r o n transfer is p r o b a b l y d e t e r m i n e d b y t h e a s i m p l e h e x a c y a n o c o m p l e x is significant as it
n a t u r e of t h e l i g a n d trans to t h e O2. s e e m s to b e g e n e r a l l y t h e c a s e that l i g a n d s s u c h as
The difficulty of assigning a formal oxi­ -
C N , w h i c h are e x p e c t e d to i n d u c e s p i n - p a i r i n g ,
dation state is more acutely seen in the f a v o u r a c o o r d i n a t i o n n u m b e r for C o 1 1
of 4 or
c a s e of 5 - c o o r d i n a t e N O a d d u c t s of t h e type 5 r a t h e r t h a n 6; the p l a n a r [Co(diars)2](C10 ) 4

[Co(NO)(salen)]. These are effectively dia­ is a further illustration of this. Presumably

magnetic a n d so h a v e n o u n p a i r e d electrons. t h e J a h n - T e l l e r distortion, w h i c h is a n t i c i p a t e d
They may therefore be formulated either as for the l o w - s p i n t\ e g
x
g configuration is largely
1 1 1 - I +
Co -NO o r C o - N O . T h e infrared a b s o r p ­ responsible.
tions a s c r i b e d to t h e N - 0 stretch lie in t h e r a n g e
_ 1
1 6 2 4 - 1 7 2 4 c m , w h i c h is at t h e l o w e r e n d of
+
t h e r a n g e said to b e c h a r a c t e r i s t i c of N O . B u t , Oxidation state I ( d ) 8

as in all s u c h c a s e s w h i c h a r e really c o n c e r n e d
w i t h t h e differing p o l a r i t i e s of c o v a l e n t b o n d s , O x i d a t i o n states l o w e r t h a n + 2 n o r m a l l y r e q u i r e
s u c h f o r m a l i s m s h o u l d n o t b e t a k e n literally. t h e stabilizing effect of 7r-acceptor l i g a n d s a n d
Other 5-coordinate Co 1 1
compounds which some of these are appropriately considered
have been characterized include [CoBr- a l o n g w i t h o r g a n o m e t a l l i c c o m p o u n d s in S e c ­
{N(C2H4NMe2) }] , 3
+
which is high-spin with tion 2 6 . 3 . 5 . E x c e p t i o n s a r e t h e s q u a r e p y r a m i d a l
3 unpaired electrons and is trigonal bipyra­ a n i o n of t h e b l a c k , M g 2 [ C o H 5 ] ( o b t a i n e d b y p r o ­
midal (imposed by the "tripod" ligand), and l o n g e d h e a t i n g of t h e p o w d e r e d m e t a l s u n d e r h i g h
 1134 Cobalt, Rhodium and Iridium Ch. 26

p r e s s u r e of H2) a n d t h e linear a n i o n of t h e gar­ excess of P P h , w a s d i s c o v e r e d

3
( 2 9 )
in 1 9 6 5 .
( 2 7 a )
net r e d C s K [ C o 0 ]
2 2(see p . 1166). H o w e v e r , It u n d e r g o e s a variety o f r e a c t i o n s , m o s t of
a l t h o u g h + 1 is n o t a c o m m o n o x i d a t i o n state for w h i c h i n v o l v e either r e p l a c e m e n t of a p h o s p h i n e
cobalt, it is o n e of the t w o m o s t c o m m o n states ligand (e.g. w i t h C O , C S , C H , 0 giving trans 2 4 2

for b o t h r h o d i u m a n d i r i d i u m a n d a s s u c h m e r i t s products) or oxidative addition (e.g. with H , 2

separate c o n s i d e r a t i o n .
S i m p l e ligand-field a r g u m e n t s , w h i c h will b e
1 1
e l a b o r a t e d w h e n M ions o f the N i , P d , P t triad
are d i s c u s s e d o n p . 1157, indicate that the d c o n ­
figuration favours a 4-coordinate, square-planar
s t e r e o c h e m i s t r y . In t h e p r e s e n t g r o u p , h o w e v e r ,
the configuration is a s s o c i a t e d w i t h a l o w e r o x i d a ­
tion state and t h e r e q u i r e m e n t s of the 18-electron
rule,^ w h i c h favour 5 - c o o r d i n a t i o n , are also t o b e
c o n s i d e r e d . T h e u p s h o t is that m o s t C o c o m p l e x e s
are 5 - c o o r d i n a t e , like [Co(CNR)5]" ", a n d s q u a r e -
1
p l a n a r C o is a p p a r e n t l y u n k n o w n . O n t h e o t h e r
1 1
h a n d , c o m p l e x e s of R h and I r are p r e d o m i n a n t l y
s q u a r e planar, a l t h o u g h 5 - c o o r d i n a t i o n d o e s also
occur.
T h e s e c o m p l e x e s a r e usually p r e p a r e d b y
the r e d u c t i o n o f c o m p o u n d s such a s R h C l . -
3 H 0 a n d K IrCl6 in t h e p r e s e n c e of t h e
2 2
desired ligand. It is often u n n e c e s s a r y t o u s e a
specific reductant, t h e ligand itself o r a l c o h o l i c
solvent b e i n g a d e q u a t e , a n d n o t infrequently
leading t o t h e p r e s e n c e of C O o r H in
the p r o d u c t . A c o n s i d e r a b l e p r o p o r t i o n of t h e
1 1
c o m p l e x e s of R h a n d I r a r e p h o s p h i n e s a n d
of these, t w o in particular d e m a n d attention.
T h e y a r e W i l k i n s o n ' s catalyst, [ R h C l ( P P h ) ] ,
and V a s k a ' s c o m p o u n d , f r a / z s - [ I r C l ( C O ) ( P P h ) ] ,
b o t h essentially s q u a r e planar.
Wilkinson s catalyst, [RhCl(PPh ) ]. T h i s red- 3 3
111
M e l ) t o f o r m R h , b u t its i m p o r t a n c e arises
from its effectiveness a s a c a t a l y s t ( 3 0 )
for h i g h l y
selective h y d r o g ι n a t i o n s of c o m p l i c a t e d o r g a n i c
s
m o l e c u l e s w h i c h a r e o f g r e a t i m p o r t a n c e in t h e
p h a r m a c e u t i c a l i n d u s t r y . Its u s e a l l o w e d , for t h e
first t i m e , r a p i d homogeneous h y d r o g ι n a t i o n at
ambient temperatures and pressures:
\ / catalyst -C O
c = c
I I
1
1 / \ H H
T h e p r e c i s e m e c h a n i s m is c o m p l i c a t e d a n d h a s
b e e n t h e subject o f m u c h s p e c u l a t i o n a n d c o n ­
t r o v e r s y , b u t F i g . 2 6 . 4 s h o w s a simplified b u t
r e a s o n a b l e s c h e m e . T h e essential steps in this
are t h e o x i d a t i v e addition o f H (if t h e h y d r o ­ 2
_
g e n a t o m s are r e g a r d e d a s " h y d r i d i c " , i.e. a s H ,
3
the m e t a l ' s o x i d a t i o n state i n c r e a s e s from + 1 t o
+ 3 ) ; t h e f o r m a t i o n of a n a l k e n e c o m p l e x ; a l k e n e
insertion a n d , finally, the r e d u c t i v e e l i m i n a t i o n of
the a l k a n e (i.e. t h e m e t a l ' s o x i d a t i o n state revert­
ing to -f-1). T h e r h o d i u m catalyst is able t o fulfil
its role b e c a u s e t h e m e t a l is c a p a b l e o f c h a n g ­
ing its c o o r d i n a t i o n n u m b e r (loss o f p h o s p h i n e
from t h e d i h y d r o c o m p l e x b e i n g e n c o u r a g e d b y
the large size of the l i g a n d ) a n d it p o s s e s s e s o x i ­
3 3
d a t i o n states ( + 1 a n d -f 3) w h i c h differ b y 2 a n d
3 2
are of c o m p a r a b l e stability.
T h e d i s c o v e r y of t h e catalytic p r o p e r t i e s

( 2 8 )
of [ R h C l ( P P h ) ] naturally b r o u g h t a b o u t a
3 3

violet c o m p o u n d , w h i c h is readily o b t a i n e d
b y refluxing e t h a n o l i c R h C l . 3 H 0 w i t h a n 3 2
^ T h e f i l l i n g - u p o f the b o n d i n g M O s o f the m o l e c u l e m a y b e
regarded, m o r e s i m p l y , a s t h e filling o f t h e o u t e r 9 orbitals
o f t h e m e t a l i o n w i t h its o w n d e l e c t r o n s p l u s a pair o f σ
8
electrons from each ligand. A 4-coordinate d i o n is thus
a " 1 6 - e l e c t r o n " s p e c i e s a n d i s " c o o r d i n a t i v e l y unsaturated".
Saturation in this s e n s e r e q u i r e s t h e a d d i t i o n o f 1 0 e l e c t r o n s ,
i.e. 5 l i g a n d s , t o t h e m e t a l i o n . B y contrast r h o d i u m ( I I I )
6
is a d ion and so can expand its c o o r d i n a t i o n
w i d e s p r e a d s e a r c h for o t h e r r h o d i u m p h o s p h i n e s
w i t h catalytic activity. O n e o f t h o s e w h i c h w a s
found, also in W i l k i n s o n ' s l a b o r a t o r y , w a s trans-
[ R h ( C O ) H ( P P h ) ] which can conveniently b e
3 3
2 8
The paramagnetic impurity w h i c h invariably a c c o m p a n i e s
W i l k i n s o n ' s c a t a l y s t h a s p r o v e d difficult t o i d e n t i f y . It i s
p r o b a b l y t h e air-stable, g r e e n , trans- [ R h C l ( C O ) ( P P h 3 ) 2 ] . s e e
K . R. D U N B A R a n d S . C . H A E F N E R , Inorg. Chem. 31, 3 6 7 6 - 9
sphere (1992).

to a c c o m m o d a t e 6 ligands with important c o n s e q u e n c e s in 2 9

J. F . Y O U N G , J. A . O S B O R N , F . H . JARDINE, and G . W I L ­
catalysis which will be seen below. K I N S O N , J. Chem. Soc, Chem. Commun., 131-2 (1965).
3 0
2 7 A
F . B E R N H A R D a n d R . H O P P E , Z. anorg. allg. Chem. 620, R. S . D I C K S O N , Homogeneous Catalysis with Compounds
187-91 (1994). of Rhodium and Iridium, D . Reidel, Dordrecht, 1 9 8 5 , 2 7 8 pp.
F i g u r e 26.4 The catalytic cycle for the hydrogιnatio n of an alkene, catalysed by [RhCl(PPh ) ] in benzene; 3 3

possible coordination of solvent molecules has been ignored and the ligand P P h has been represented 3

as Ρ throughout, for clarity.

dealt w i t h h e r e . It w a s f o u n d that, for steric T h e r e a s o n for its selectivity lies in the insertion
r e a s o n s , it s e l e c t i v e l y c a t a l y s e s t h e h y d r o g ι n a t i o n s t e p of the c y c l e . In t h e p r e s e n c e of t h e t w o
of alk-l-enes (i.e. terminal olefins) rather b u l k y P P h g r o u p s , the a t t a c h m e n t to the m e t a l of
3

than alk-2-enes and it h a s b e e n used in the - C H C H R (anti-Markovnikov addition, leading

2 2

hydroformylation of a l k e n e s , (i.e. the a d d i t i o n of to a straight chain product) is easier than

H a n d t h e f o r m y l g r o u p , C H O ) a l s o k n o w n as the a t t a c h m e n t of -CH(CH )R 3 (Markovnikov
t h e O X O p r o c e s s b e c a u s e it i n t r o d u c e s o x y g e n addition, leading to a branched-chain product).
into the hydrocarbon. This is a process of Vaska's compound, trans-[IrCl(CO)(PPh )2]- 3

e n o r m o u s industrial i m p o r t a n c e , b e i n g u s e d t o T h i s y e l l o w c o m p o u n d c a n b e p r e p a r e d b y the
c o n v e r t alk-1 - e n e s into a l d e h y d e s w h i c h c a n t h e n r e a c t i o n of t r i p h e n y l p h o s p h i n e a n d I r C l 3 in a
b e c o n v e r t e d t o a l c o h o l s for t h e p r o d u c t i o n of solvent s u c h as 2 - m e t h o x y e t h a n o l which acts
polyvinylchloride (PVC) and polyalkenes and, b o t h as r e d u c i n g a g e n t a n d s u p p l i e r of C O . It
in the c a s e of the l o n g - c h a i n a l c o h o l s , in the w a s d i s c o v e r e d in 1961 b y L. V a s k a a n d J. W . di
p r o d u c t i o n of d e t e r g e n t s : Luzio ( 3 1 ) a n d r e c o g n i z e d as an ideal material
for the s t u d y of o x i d a t i v e addition reactions,
catalyst
RCH=CH 2 + H 2 + CO • RCH CH CHO 2 2
s i n c e its p r o d u c t s are g e n e r a l l y stable a n d readily
c h a r a c t e r i z e d . It is c e r t a i n l y the m o s t t h o r o u g h l y
A simplified reaction scheme is shown in i n v e s t i g a t e d c o m p o u n d of I r . It f o r m s o c t a h e d r a l
1

Fig. 26.5 Again, the ability of rhodium to Ir 111 c o m p l e x e s in o x i d a t i v e a d d i t i o n reactions

c h a n g e its c o o r d i n a t i o n n u m b e r a n d oxidation with H , C l , H X , M e l and R C 0 H , and ' H n m r
2 2 2

state is c r u c i a l , a n d this c a t a l y s t h a s t h e g r e a t s h o w s that in all c a s e s the p h o s p h i n e l i g a n d s are

advantage over the conventional cobalt carbonyl trans to e a c h other. T h e 4 r e m a i n i n g l i g a n d s (CI,
catalyst that it o p e r a t e s efficiently at m u c h l o w e r
t e m p e r a t u r e s a n d p r e s s u r e s a n d p r o d u c e s straight- 3 1 L . V A S K A a n d J. W . D i L u z i o , J. Am. Chem. Soc. 83,
c h a i n as o p p o s e d t o b r a n c h e d - c h a i n products. 2 7 8 4 - 5 (1961).
Figure 26.5 The catalytic cycle for the hydroformylation of an alkene catalysed by r r a « 5 - [ R h H ( C O ) ( P P h ) ] . The 3 3

tertiary phosphine ligand has been represented as Ρ throughout.

C O a n d t w o c o m p o n e n t s of the r e a c t a n t ) t h e r e f o r e theoretical models have been suggested to

lie in a p l a n e a n d 3 i s o m e r s are p o s s i b l e : a c c o u n t for t h i s . ( 3 2 )

A d d i t i o n r e a c t i o n s w i t h l i g a n d s s u c h as C O
a n d SO2 (the a d d i t i o n of w h i c h as an u n c h a r g e d
l i g a n d is u n u s u a l ) differ in that n o oxidation
o c c u r s a n d 5 - c o o r d i n a t e 18-electron Ir 1 products
are f o r m e d .
T h e r e is a p p a r e n t l y n o s i m p l e w a y of p r e d i c t i n g T h e facile absorption of O2 b y a solution
w h i c h of t h e s e will b e f o r m e d a n d e a c h c a s e of Vaska's compound is accompanied by a
must be examined individually. The situation c h a n g e in c o l o u r f r o m y e l l o w to o r a n g e w h i c h
is further c o m p l i c a t e d b y t h e fact that, when may be reversed by flushing with N2. This
t h e CI of V a s k a ' s compound is r e p l a c e d by
H , M e o r P h , a d d i t i o n of H 2 gives products 3 2 M . J. B U R K , M . P. MCGRATH, R. WHEELER and
in w h i c h the p h o s p h i n e s are n o w cis. Various R . H . C R A B T R E E , J. Am. Chem. Soc. 110, 5 0 3 4 - 9 (1988).
§26.3.3 Complexes 1137

is o n e of the most widely studied synthetic reactions with P ( 0 M e ) 3 and P ( 0 E t ) 3 give both
oxygen-carrying systems and has been discussed paramagnetic monomers [Co°{P(OR) } ], 3 4 and
earlier (p. 6 1 5 ) . T h e 0 - 0 d i s t a n c e of 130 p m in d i a m a g n e t i c d i m e r s [ C o ^ P i O R ^ J s ] , w h e r e a s the
the oxygenated product (see Fig. 14.5b, p. 617) more bulky P(0Pr*)3 yields only the orange-
is r a t h e r c l o s e to t h e 128 p m of t h e s u p e r o x i d e red monomeric product. With an excess of
ion, 0 2 _ , b u t this w o u l d i m p l y I r 11 which is s o d i u m a m a l g a m as r e d u c i n g a g e n t t h e prod­
p a r a m a g n e t i c w h e r e a s t h e c o m p o u n d is a c t u a l l y u c t w i t h this latter l i g a n d is t h e w h i t e - c r y s t a l l i n e
d i a m a g n e t i c . T h e o x y g e n a t i o n is i n s t e a d n o r m a l l y N a [ C o - { P ( O P r ) } ] . In v i e w of the r e a d y sol­
I , 3 5

treated as a n o x i d a t i v e addition with the 0 2 ubility of this c o m p o u n d in p e n t a n e a n d t h e d 1 0

acting as a b i d e n t a t e peroxide ion, 0 2 2 _ , to c o n f i g u r a t i o n of C o - 1 it m a y b e that o n l y 4 of

give a 6-coordinate I r m product. However, in t h e p h o s p h i t e l i g a n d s a r e directly coordinated
view of the small " b i t e " of this ligand the to the metal centre: one possible formulation
a l t e r n a t i v e f o r m u l a t i o n in w h i c h t h e 0 2 acts as would be
a neutral unidentate ligand giving a 5-coordinate
Ir p r o d u c t h a s a l s o b e e n p r o p o s e d .
1

O x y g e n - c a r r y i n g p r o p e r t i e s a r e e v i d e n t l y criti­
cally d e p e n d e n t o n t h e p r e c i s e c h a r g e d i s t r i b u t i o n
a n d steric factors w i t h i n t h e m o l e c u l e . R e p l a c e ­
m e n t of t h e CI in V a s k a ' s c o m p o u n d w i t h I c a u s e s
loss of o x y g e n - c a r r y i n g ability, t h e o x y g e n a t i o n
being irreversible. This can be rationalized by
n o t i n g that t h e l o w e r e l e c t r o n e g a t i v i t y of the
iodine would allow a greater electron density on
the m e t a l , t h u s facilitating Μ —> 0 2 π donation:
this i n c r e a s e s t h e s t r e n g t h of t h e M - 0 2 bond and,
b y p l a c i n g c h a r g e in a n t i b o n d i n g orbitals of t h e
With the terdentate P-donor ligand, MeC-
0 , c a u s e s a n i n c r e a s e in t h e 0 - 0 d i s t a n c e f r o m
2

(CH PPh )3,

2 2 (tppme) excess sodium amalgam
130 to 1 5 1 p m .
a n d a n a t m o s p h e r e of N 2 yields the deep-brown
[ ( t p p m e ) C o - N - N - C o ( t p p m e ) ] which, unusually
for a dimer, is paramagnetic. ( 3 3 ) The N-N
Lower oxidation states d i s t a n c e in t h e l i n e a r b r i d g e is 118 p m c o m p a r e d
w i t h 109.8 p m in N 2 (p. 412).
Numerous complexes of Co, Rh and Ir are A n o t h e r t e c h n i q u e for o b t a i n i n g l o w o x i d a t i o n
known in which the formal oxidation state states is b y e l e c t r o l y t i c r e d u c t i o n u s i n g cyclic
of the metal is zero, — 1 , or even lower. voltametry. Some spectacular series can be
M a n y of t h e s e c o m p o u n d s c o n t a i n C O , C N ~ o r a c h i e v e d of w h i c h , p e r h a p s , t h e m o s t n o t a b l e is
R N C as l i g a n d s a n d so a r e m o r e conveniently b a s e d o n [ I r ( b i p y ) 3 ] " " : this, w h e n d i s s o l v e d in
III 3 1

discussed under organometallic compounds (Sec­ M e C N , c a n b e o x i d i z e d to [ I r ( b i p y ) ] I V 3 4 + and

tion 2 6 . 3 . 5 ) . H o w e v e r , o t h e r l i g a n d s s u c h as ter­ r e d u c e d in s u c c e s s i v e 1-electron steps to g i v e
tiary p h o s p h i n e s a l s o stabilize t h e l o w e r o x i d a t i o n e v e r y o x i d a t i o n state d o w n to [Ir _ I I 1 (bipy)3] , 3 -

states, as exemplified by the brown, tetra­ a total of 8 interconnected redox complexes.

hedral, paramagnetic complex [Co°(PMe3)4]: H o w e v e r , b y n o m e a n s all h a v e b e e n isolated
this is made by reducing an ethereal solu­ as solid products from solution. Many other
tion of CoCl 2 with Mg or Na amalgam in
the presence of PMe3. Further treatment of
3 3 F. C E C C O N I , C. A. GHILARDI, S. M I D O L L I N I , S. MONETI,
the product with Mg/thf in the presence of A . O R L A N D I N I a n d M . B A C C I , J. Chem. Soc, Chem. Commun.,
N 2 gives [ M g ( t h f ) 4 ] [ C o - ( N ) ( P M e 3 ) 4 ] . Similar
n 2 731-3 (1985).
1138 Cobalt, Rhodium and Iridium Ch. 26

s u c h r e d o x series a r e k n o w n for t h e s e a n d o t h e r
elements.

26.3.4 The biochemistry of cobalt^

T h e w a s t i n g d i s e a s e in s h e e p a n d cattle k n o w n
variously as " p i n e " (Britain), "bush sickness"
(New Zealand), "coast disease" (Australia), a n d
"salt s i c k " ( F l o r i d a ) h a s b e e n r e c o g n i z e d s i n c e
t h e late e i g h t e e n t h c e n t u r y . W h e n it w a s r e a l i z e d
to b e a n a n a e m i c c o n d i t i o n it w a s t h o u g h t t o
b e d u e t o iron deficiency a n d w a s therefore
treated, w i t h m i x e d s u c c e s s , b y a d m i n i s t e r i n g
iron salts. T h e n , in t h e 1930s, it w a s f o u n d
b y w o r k e r s i n A u s t r a l i a a n d N e w Z e a l a n d that
t h e efficacious p r i n c i p l e in t h e iron treatment
was actually an impurity (cobalt) b u t its role
was not understood. This became more evident (b)

w h e n v i t a m i n Β12 w a s e x t r a c t e d f r o m r a w liver
F i g u r e 26.6 Vitamin B j : (a) a corrin ring showing
2
and shown to b e responsible for the latter's
a square-planar set of Ν atoms and
w e l l - k n o w n effectiveness i n t r e a t i n g p e r n i c i o u s a replaceable H, and (b) simplified
anaemia. It is n o w k n o w n that v i t a m i n Β12 structure of B i . In view of the 2

is a c o e n z y m e ^ in a n u m b e r o f b i o c h e m i c a l Η displaced from the corrin ring,

p r o c e s s e s , t h e m o s t i m p o r t a n t of w h i c h is t h e the C o - C bond, and the charge on
the ribose phosphate, the cobalt is
formation of e r y t h r o c y t e s ( r e d b l o o d - c e l l s ) . It
formally in the + 3 oxidation state. This
obviously functions extremely effectively, t h e and related molecules are conveniently
human body for i n s t a n c e containing a mere represented as: R
2 - 5 m g , c o n c e n t r a t e d in t h e liver.
j—[Co 1 1 1 !
T h e structure o f t h e d i a m a g n e t i c , c h e r r y - r e d
v i t a m i n Β12 is s h o w n i n F i g . 2 6 . 6 a n d it c a n
be seen that the coordination sphere of the difference is a p p a r e n t , however, in t h e sixth
c o b a l t h a s m a n y similarities w i t h that o f iron c o o r d i n a t i o n p o s i t i o n w h i c h , i n h a e m o g l o b i n , is
in haem (see Fig. 25.7). In both cases the e i t h e r v a c a n t o r o c c u p i e d b y O2. H e r e it is filled
m e t a l is c o o r d i n a t e d t o 4 n i t r o g e n a t o m s o f a n by a σ-bonded c a r b o n , ( 3 5 ) m a k i n g v i t a m i n Β12
u n s a t u r a t e d m a c r o c y c l e (in this c a s e p a r t of a t h e first, a n d s o far t h e o n l y , fully established
" c o r r i n " r i n g w h i c h i s less s y m m e t r i c a l a n d n o t naturally occurring organometallic compound.
s o u n s a t u r a t e d a s t h e p o r p h y r i n in h a e m ) w i t h a n T h e u s u a l m e t h o d s of isolation l e a d t o a p r o d u c t
i m i d a z o l e n i t r o g e n in t h e fifth p o s i t i o n . A m a j o r k n o w n a s cyanocobalamin, w h i c h is t h e s a m e
as vitamin Β12 itself but with C N ~ instead
3 4 W . K A I M and B . SCHWERDERSKI, pp. 3 9 - 5 5 of Bioinor- of deoxyadenosine in t h e sixth coordination
ganic Chemistry .'Inorganic Elements in the Chemistry of Life, p o s i t i o n . T h i s is a labile site, a n d o t h e r d e r i v a t i v e s
W i l e y , C h i c h e s t e r , 1 9 9 4 ; L . R . M I L G R O M , Chem. in Brit. 3 1 ,
s u c h a s aquocobalamin can b e prepared.
9 2 3 - 7 (1994).
^ E n z y m e s are proteins w h i c h act a s very specific catalysts Incorporation of cobalt into the corrin ring
in b i o l o g i c a l s y s t e m s . T h e i r a c t i v i t y m a y d e p e n d o n t h e system modifies the reduction potentials of
presence o f substances, often metal c o m p l e x e s , o f m u c h
l o w e r m o l e c u l a r w e i g h t . T h e s e a c t i v a t o r s are k n o w n a s
"coenzymes". D . C . H O D G K I N , Proc. Roy. Soc. A 288, 2 9 4 - 3 0 5 (1965).
§26.3.5 Organometallic compounds 1139

Β i2s, a r e a m o n g s t t h e m o s t p o w e r f u l n u c l e o p h i l e s
known (hence, "supernucleophiles"), liberating
H 2 from water.
Virtually all the biological processes, in
w h i c h v i t a m i n Β12 is a c t i v e , i n v o l v e s u b s t i t u e n t
e x c h a n g e of t h e t y p e :

H R R H

I I I I
-c—c- -c—c-

w h i c h , significantly, d o e s n o t i n v o l v e s o l v e n t p r o ­
t o n s . T h e p r e c i s e m e c h a n i s m of t h e s e r e a c t i o n s is
n o t settled b u t all i n v o l v e c l e a v a g e of t h e C o - C
b o n d a n d it is e v i d e n t from t h e s t u d y of m o d e l
s y s t e m s that t h e l a c k of c o m p l e t e p l a n a r i t y of t h e
c o r r i n ring is an i m p o r t a n t factor in c o n t r o l l i n g
F i g u r e 26.7 Model vitamin Β π compounds: (a) a this. ( 3 6 )

Schiff base derivative, and (b) a cobal-

oxime, in this case derived from
dimethylglyoxime.
26.3.5 Organometallic compounds^

c o b a l t g i v i n g it t h r e e a c c e s s i b l e a n d c o n s e c u t i v e M a n y of the o r g a n o m e t a l l i c c o m p o u n d s of t h e
o x i d a t i o n states: e l e m e n t s of this g r o u p s h o w v a l u a b l e catalytic
OH activity a n d , as d i s c u s s e d a b o v e , m u c h of t h e
c h e m i s t r y of v i t a m i n Β12 is t h e c h e m i s t r y of
[Com] [Co"]
the Co-Co bond. Simple homoleptic alkyls
and aryls of cobalt, [CoRJ, have not in
Hydroxocobalamin Vitamin B
l2r
fact b e e n p r e p a r e d , b u t this is e v i d e n t l y not
purple brown
d u e to t h e r m o d y n a m i c instability of t h e Co-C
/II
bond. C o m p o u n d s containing such bonds can be
+e~ p r e p a r e d in a b u n d a n c e , n o t o n l y w i t h ( σ + π ) -
b o n d i n g l i g a n d s s u c h as p h o s p h i n e s a n d C O b u t
I [Col] a l s o w i t h non-7r-bonding l i g a n d s s u c h as Schiff
b a s e s a n d g l y o x i m e s . T h e s e latter presumably
Vitamin B 1 2 s

blue-green o w e their e x i s t e n c e n o t t o e l e c t r o n i c b u t r a t h e r
to steric factors, t h e a d d i t i o n a l l i g a n d s b l o c k i n g
T h e r e d u c t i o n s are effected in n a t u r e b y
what might otherwise be energetically favourable
ferredoxin (p. 1102). T h i s b e h a v i o u r c a n b e
decomposition paths.
reproduced surprisingly well by simpler, model
c o m p o u n d s . S o m e of t h e b e s t k n o w n of t h e s e
a r e o b t a i n e d b y t h e a d d i t i o n of axial g r o u p s 3 6 M. RAVIKANTH and T. K. CHANRESHEKAR, Structure and
Bonding, 82, 1 0 5 - 8 8 (1995).
to t h e s q u a r e - p l a n a r c o m p l e x e s of C o with 1 1

3 7 R . S . DICKSON, Organometallic Chemistry of Rhodium

Schiff b a s e s , o r s u b s t i t u t e d g l y o x i m e s ( g i v i n g
and Iridium, A c a d e m i c Press, N e w York, 1983, 4 3 2 pp.;
c o b a l o x i m e s ) as illustrated in F i g . 2 6 . 7 . T h e C. W H I T E , Organometallic Compounds of Cobalt, Rhodium
r e d u c e d C o s p e c i e s of t h e s e , a l o n g w i t h v i t a m i n
1 and Iridium, C h a p m a n & Hall, L o n d o n 1985, 2 9 6 pp.
1140 Cobalt, Rhodium and Iridium Ch. 26

Carbonyls (see p. 926) 51°C. T h e structure, which involves t w o bridging

carbonyl groups as shown in F i g . 2 6 . 8 a , c a n
B e c a u s e t h e y p o s s e s s a n o d d n u m b e r of v a l e n c e perhaps b e most easily rationalized o n the basis
e l e c t r o n s t h e e l e m e n t s of this g r o u p c a n o n l y of a " b e n t " C o - C o b o n d a r i s i n g f r o m o v e r l a p of
satisfy t h e 18-electron r u l e in their carbonyls angled metal orbitals ( d s p 2 3
hybrids). However,
if M - M bonds are present. In accord with in s o l u t i o n this s t r u c t u r e is in e q u i l i b r i u m w i t h a
this, mononuclear carbonyls are not formed. second form (Fig. 26.8b) which h a s n o bridging
Instead [ M ( C O ) ] , [ M ( C O ) ] a n d [ M ( C O ) ]
2 8 4 1 2 6 1 6 carbonyls a n d is h e l d together solely by a
are the principal binary carbonyls of these C o - C o bond.
elements. But reduction of [ C o ( C O ) g ]
2 with, T h e m o s t s t a b l e c a r b o n y l s of r h o d i u m a n d irid­
for i n s t a n c e , s o d i u m a m a l g a m in b e n z e n e y i e l d s i u m a r e r e s p e c t i v e l y r e d a n d y e l l o w solids o f t h e
the m o n o m e r i c a n d tetrahedral, 18-electron ion, form [ M ( C O ) i ] which are obtained b y heat­
4 2

[Co(CO)4]~, acidification of w h i c h gives the ing MCI3 with copper metal under about 200 atm
pale yellow hydride, [HCo(CO)4]. Reductions of C O . T h e b l a c k c o b a l t a n a l o g u e is m o r e s i m ­
e m p l o y i n g N a m e t a l i n liquid NH3 yield the ply o b t a i n e d b y h e a t i n g [ C o ( C O ) g ] in a n inert
2

3
"super-reduced" [ M ( C O ) ] ~ ( M = C o , R h , Ir)
3 atmosphere
c o n t a i n i n g t h e s e e l e m e n t s in their l o w e s t f o r m a l
( 3 8 )
oxidation s t a t e . 2[Co (CO) ] 2 8 [Co (CO) ] + 4CO
4 1 2

The importance of cobalt carbonyls lies in

T h e s t r u c t u r e s a r e s h o w n in F i g . 2 6 . 8 c a n d d a n d
their i n v o l v e m e n t in h y d r o f o r m y l a t i o n reactions
differ in that, w h e r e a s t h e I r c o m p o u n d c o n s i s t s
d i s c u s s e d a b o v e . T h e o r i g i n a l , a n d still w i d e l y
of a t e t r a h e d r o n of m e t a l a t o m s h e l d together
used, process depends on the u s e of cobalt
solely b y M - M b o n d s , t h e R h a n d C o c o m p o u n d s
salts r a t h e r t h a n t h e n e w e r r h o d i u m catalysts
each incorporate 3 bridging carbonyls. A similar
(pp. 1 1 3 4 - 5 ) . The mechanism of the cobalt
difference w a s n o t e d in t h e c a s e of t h e t r i n u c l e a r
c y c l e is m o r e difficult t o a s c e r t a i n b u t it s e e m s
carbonyls of F e , R u and O s (p. 1104) and
clear that the active agent is t h e hydride, ( 3 9 )
c a n b e e x p l a i n e d in a s i m i l a r w a y . T h e M4
[ H C o ( C O ) 4 ] . It i s , m o r e o v e r , p l a u s i b l e that t h e
t e t r a h e d r a of C o a n d R h a r e s m a l l e n o u g h t o
c y c l e is b a s i c a l l y t h e s a m e a s that o u t l i n e d in
b e a c c o m m o d a t e d in a n i c o s a h e d r a l a r r a y of C O
F i g . 2 6 . 5 b u t starting with loss of C O from
l i g a n d s w h e r e a s t h e l a r g e r I r 4 t e t r a h e d r o n forces
[ H C o ( C O ) 4 ] r a t h e r t h a n loss o f p h o s p h i n e f r o m
t h e a d o p t i o n of t h e less d e n s e c u b e o c t a h e d r a l
[ R h ( C O ) H ( P P h 3 ) 3 ] , so producing a comparable
array of ligands.
coordinatively unsaturated intermediate to which
Of the [ M 6 ( C O ) i 6 ] carbonyls the very dark-
t h e a l k e n e c a n a t t a c h itself. T h e d i s a d v a n t a g e s
brown Rh compound prepared simultaneously
of t h e s y s t e m , as already mentioned, a r e its
with and separated from [Rli4(CO)i ] 2 is t h e
l a c k of specificity, leading to branched-chain
b e s t k n o w n . I n t h e solid its s t r u c t u r e consists
p r o d u c t s , a n d t h e n e c e s s i t y of h i g h t e m p e r a t u r e s
of a n o c t a h e d r a l a r r a y o f R h ( C O ) 2 units with
( > 1 5 0 ° C ) a n d pressure ( ~ 2 0 0 atm). In addition
t h e r e m a i n i n g 4 C O ' s b r i d g i n g 4 faces of t h e
the volatility of [ H C o ( C O ) 4 ] poses recovery
octahedron (Fig. 26.8e). A black isomorphous,
problems.
and presumably isostructural, C o analogue and
The dinuclear octacarbonyls are obtained by an isostructural red Ir analogue are known. A
h e a t i n g t h e m e t a l ( o r in t h e c a s e of i r i d i u m , second, black Ir isomer occurs which differs
I1CI3 -I- c o p p e r m e t a l ) u n d e r a h i g h p r e s s u r e of o n l y in that it h a s 4 e d g e - b r i d g i n g r a t h e r t h a n
C O ( 2 0 0 - 3 0 0 atm). C o ( C O ) 2 8 is b y far t h e b e s t face-bridging C O groups. Again rationalization
known, the other two being poorly characterized; is p o s s i b l e o n t h e b a s i s o f t h e l i g a n d p o l y h e d r a l
it is a n a i r - s e n s i t i v e , o r a n g e - r e d solid m e l t i n g at
3 9
B . F. G. J O H N S O N and Y. V. ROBERTS, Polyhedron, 12,
J . E . E L L I S , Adv. Organometallic Chem., 31, 1 - 5 2 (1990). 9 7 7 - 9 0 (1993).
§26.3.5 Organometallic compounds 1141

F i g u r e 26.8 Molecular structures of some binary carbonyls of Co, Rh, and Ir. (a) C o ( C O ) 8 in solid state, showing 2

the formation of a "bent" C o - C o bond, (b) C o ( C O ) in solution, (c) I r ( C O ) i . (d) M ( C O ) i ,

2 8 4 2 4 2

M = Co, Rh. (e) M ( C O ) i 6 M = Co, Rh and Ir (for its red isomer), (f) black isomer of I r ( C O ) .
6 6 16

m o d e l . In both structures the ligands occupy the c e n t r e d c u b i c lattices s t a b i l i z e d b y C O l i g a n d s .

16 v e r t i c e s of a t e t r a c a p p e d t r u n c a t e d t e t r a h e d r o n . [ R h H ( C O ) 2 ] ~ ( F i g 2 6 . 9 a ) is t y p i c a l .
1 3 3 4 2

In o n e c a s e t h e 4 c a p s a r e t h e f a c e - b r i d g i n g T h e a n i o n i c c l u s t e r [ I r 6 ( C O ) i 5 ] ~ is o c t a h e d r a l
2

l i g a n d s , in t h e o t h e r t h e e d g e - b r i d g i n g l i g a n d s . and an increasing n u m b e r of Ir clusters have been

T h e two structures are related by a simple rotation reported recently though their preparations are
of t h e M6 o c t a h e d r o n a b o u t a C 4 axis. ( 3 9 ) m o r e difficult a n d y i e l d s u s u a l l y s m a l l e r t h a n f o r
Carbonyl hydrides and carbonylate anions rhodium. [ I r i ( C O ) 2 7 ] ~ has the highest nuclearity
4

are obtained by reducing neutral carbonyls, so far a n d is o b t a i n e d as black crystals b y

as mentioned above, and in addition to oxidizing [ I r 6 ( C O ) i 5 ] ~ 2 with ferricinium ion ( 4 0 )

m o n o n u c l e a r m e t a l a n i o n s , a n i o n i c s p e c i e s of (Fig 26.9b).
very high nuclearity have been obtained, often T h e i n c o r p o r a t i o n of interstitial o r e n c a p s u l a t e d
by thermolysis. These are especially numerous h e t e r o a t o m s is a c o m m o n a n d s t a b i l i z i n g feature.
for R h a n d in c e r t a i n R h n , R h i 4 a n d Rhi5 a n i o n s C a r b o n is t h e m o s t c o m m o n a n d , a s is t h e c a s e in
have structures conveniently visualized either as
p o l y h e d r a e n c a p s u l a t i n g further m e t a l a t o m s , o r
4 0 R . D . PERGOLA, L . GARLASCHELLI, M . MANASSERO,
a l t e r n a t i v e l y a s a r r a y s of m e t a l a t o m s forming N. MASCIOCCHI and P . ZANELLO, Angew. Chem. Int. Edn.
portions of h e x a g o n a l close packed or body Engl. 32, 1347-9 (1993).
 1142 Cobalt, Rhodium and Iridium Ch. 26

F i g u r e 26.9 Schematic representations of the metal cores of some clusters of group 9 metals.
2 2 _
( a ^ [ R h i 3 H ( C O ) 2 4 ] ~ ; the H atoms migrate within the cluster, (b) [ I r ( C O ) ] ~ . (c) [ R h C ( C O ) i ] .
3 l4 27 6 5

(d) [ R h C ( C O ) i 9 ] ; a trigonal prism of 6 Rh atoms has one face capped by a seventh Rh atom
8

2
and one edge bridged by the eighth Rh atom, (e) [Co C(CO)i8] ~~; the 8 Co atoms define a 8

distorted bicapped trigonal prism which, alternatively, can be viewed as a distorted square antiprism.
(f) [ R h ( C ) ( C O ) ] .
l2 2 25

g r o u p 8 (p. 1 1 0 7 ) , m a y o r i g i n a t e f r o m t h e s o l v e n t C a t o m s : [ R h i ( C ) ( C O ) 5 ] ( F i g . 26.9f h a s
2 2 2 no
o r f r o m x l e a v a g e of a C O l i g a n d . T h e c a r b i d o C s y m m e t r y e l e m e n t s b u t it is c l e a r that t h e R h i 2

contributes 4 electrons to the cluster bonding and cluster surrounds an ethanide unit C 2 in w h i c h t h e
2
in t h e 9 0 - e l e c t r o n s p e c i e s [ R h 6 C ( C O ) i 5 ] ~ fea­ C - C d i s t a n c e is o n l y 147 p m ) ; t h e c l u s t e r a l s o h a s
t u r e s t r i g o n a l p r i s m a t i c c o o r d i n a t i o n of R h ι a b o u t 14 p e n d a n t t e r m i n a l C O g r o u p s , 10 μ - C O g r o u p s
the central C (Fig. 26.9c). M o r e complex g e o m e ­ a n d o n e ^ - C O . In c o n t r a s t ,
3 [Rh (C) (CO) ]
1 5 2 2 8

tries a r e f o u n d for [Rh C(CO)i ] 8 9 (Fig. 26.9d) has individual 6-coordinate (octahedral) carbido
2
and [ C o C ( C O ) i ] - (Fig. 26.9e): these t w o iso-
8 8 C a t o m s s y m m e t r i c a l l y p l a c e d o n e a c h side of a
electronic clusters are not isostructural though a c e n t r a l R h w h i c h itself h a s 12 R h n e a r e s t n e i g h ­
slight d i s t o r t i o n w o u l d ( h y p o t h e t i c a l l y ) t r a n s f o r m b o u r s in a d d i t i o n t o t h e 2 C a t o m s . A g a i n , t h e
o n e i n t o t h e o t h e r . T h e c e n t r a l c a r b i d o C in t h e a p p r o a c h t o m e t a l s t r u c t u r e s is n o t a b l e a n d is o n e
2
s q u a r e a n t i p r i s m a t i c [ C o C ( C O ) i ] ~ is f o r m a l l y
8 8 of t h e m a i n interests in c o n s t r u c t i n g l a r g e c l u s t e r s
8 - c o o r d i n a t e , t h e C o - C d i s t a n c e s b e i n g in t h e a n d s t u d y i n g t h e i r c h e m i c a l a n d c a t a l y t i c activity.
r a n g e 1 9 5 - 2 2 0 p m w i t h a m e a n v a l u e of 2 0 7 p m . H , P , A s , S h a v e a l s o b e e n e n c a p s u l a t e d in i o n s
Even more complicated structures are found such as [Rh (H) (CO) ] -,
1 3 3 2 4
2
[Rh P(CO) ] -
9 2 1
2

for t h e l a r g e R h c l u s t e r s c o n t a i n i n g 2 c a r b i d o [Rh As(CO) ] -

1 0 2 2
3
and [Rh (S) (CO) ] -.
1 7 2 3 2
3
§26.3.5 Organometallic compounds 1143

More recently Ν has been encapsulated^ 1 )

in thf. H a v i n g 1 m o r e e l e c t r o n t h a n f e r r o c e n e ,
2 2 5
2
in [ R h ( N ) ( C O ) ] - a n d [ R h ( N ) ( C O ) 8 ] - .
1 4 2 3 4 3
3
it is p a r a m a g n e t i c w i t h a m a g n e t i c m o m e n t of
T h e latter is t h e largest R h c l u s t e r s o far c h a r a c ­ 1.76 B M a n d , w h i l e it is t h e r m a l l y s t a b l e up
terized. It c o n s i s t s of a n i r r e g u l a r p o l y h e d r o n of t o 2 5 0 ° C , its m o s t o b v i o u s c h a r a c t e r i s t i c is its
2 1 R h a t o m s e n c a p s u l a t i n g a p a i r of p a r t i c u l a r l y r e a d y loss of this e l e c t r o n t o f o r m t h e y e l l o w -
m 5 +

c l o s e ( 2 5 7 . 1 p m ) R h a t o m s as w e l l as 4 Ν a t o m s green cobalticenium ion, [Co (?7 -C5H5) ] . 2

e a c h of w h i c h is l o c a t e d in a s e m i o c t a h e d r a l site. T h i s resists further o x i d a t i o n , b e i n g s t a b l e e v e n in

Other derivatives of the carbonyls are of cone H N 0 3 b u t , like t h e i s o e l e c t r o n i c f e r r o c e n e ,
course numerous; Ir forms many carbonyl is s u s c e p t i b l e to n u c l e o p h i l i c a t t a c k o n its rings.
5
I
h a l i d e s of t h e t y p e s [ I r ( C O ) X ] , [ I r ^ C O ) ^ ] " ,
3
R h o d o c e n e , [ R h ( ? 7 - C 5 H 5 ) ] , is a l s o k n o w n b u t
2

m
[Ir (CO) X ]- 2 4 and [Ii^CO^] ", 2
but the is u n s t a b l e t o o x i d a t i o n a n d h a s a t e n d e n c y t o
stability of c a r b o n y l halides falls off in the f o r m d i m e r i c s p e c i e s . C l a i m s for the e x i s t e n c e
m

s e q u e n c e Ir > R h > C o a n d t h o s e of C o a r e o n l y of i r i d o c e n e p r o b a b l y refer to I r complexes.

of t h e t y p e [ C o ( C O ) X ] a n d a r e v e r y u n s t a b l e .
4
T h e b u l k of d e r i v a t i v e s a r e o b t a i n e d b y t h e d i s ­
p l a c e m e n t of C O b y o t h e r l i g a n d s . T h e s e i n c l u d e
p h o s p h i n e s a n d o t h e r g r o u p 15 d o n o r s , N O , m e r -
captans and unsaturated organic molecules such
as a l k e n e s , a l k y n e s a n d c y c l o p e n t a d i e n y l s .
H o w e v e r , t h e y e l l o w r h o d i c e n i u m a n d iridice-
n i u m c a t i o n s a r e c e r t a i n l y k n o w n a n d a r e entirely
a n a l o g o u s t o t h e c o b a l t i c e n i u m c a t i o n in their
r e s i s t a n c e to o x i d a t i o n a n d susceptibility t o n u c l e ­
o p h i l i c attack.
N u m e r o u s " h a l f - s a n d w i c h " c o m p o u n d s of t h e
5
t y p e [ M ( r η - C R ) L ] , M = R h , Ir; R = H , M e ;
5 5 2

L = CO, phosphine etc.) are k n o w n and are

Cyclopentadienyls
5
useful r e a g e n t s . [ I r ( ? 7 - C 5 M e 5 ) ( C O ) ] for i n s t a n c e 2

is a n e x c e l l e n t n u c l e o p h i l e a n d is a l s o u s e d in
n 5
C o b a l t o c e n e , [ C o ( r ; - C 5 H 5 ) ] , is a d a r k - p u r p l e
2 t h e p h o t o c h e m i c a l a c t i v a t i o n of C - H in a l k a n e s .
air-sensitive material, prepared by the reactions It is p a r t i c u l a r l y effective in the latter r o l e w h e n
( 4 2 )
of s o d i u m c y c l o p e n t a d i e n e a n d a n h y d r o u s C o C l 2
supercritical C 0 2 is t h e s o l v e n t .

4 2
4 1
S. M A I O T N E N G O , G. C I A N I and A. S I R O N I , J. Chem. Soc, M . J O B L I N G , S . M . H O W D L E , M . A . H E A L Y and M. POLIA-

Chem. Commun., 1 4 0 5 - 6 (1992). KOFF, J. Chem. Soc, Chem. Commun., 1 2 8 7 - 9 0 (1990).