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To cite this Article Stern, Eric W.(1968) 'Reactions of Unsaturated Ligands in Pd(II) Complexes', Catalysis Reviews, 1: 1, 73
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Reactions of Unsaturated
Ligands in Pd(ll] Complexes
ERIC W . STERN
The M . W. Kellogg Company
Division of Pullman. Inc .
Piscataway. New J e r s e y
. ...........................
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I INTRODUCTION 74
I1. REACTIONS O F OLEFINS ..................... 75
A . Nucleophilic Reactions: Aqueous Systems . . . . . . . . 75
8. Nucleophilic Reactions: Nonaqueous Systems ...... 89
C . Double-Bond Isomerization . . . . . . . . . . . . . . . . . . 108
.....................
D . Condensation Reactions 113
. ...............................
E T-AllylS 114
. ...........................
F Hydrogenation 117
I11. REACTIONS O F ACETYLENES . . . . . . . . . . . . . . . . . . 117
IV . REACTIONS O F AROMATICS . . . . . . . . . . . . . . . . . . . 119
.
V REACTIONS O F OLEFINICALLY UNSATURATED COM-
POUNDS CONTAINING OTHER FUNCTIONAL GROUPS . . 121
.
A Reactions of a.@-Unsaturated Compounds . . . . . . . . . 122
.
B Reactions of P. Y-Unsaturated Compounds ......... 126
.
VI REACTIONS O F CARBON MONOXIDE ............. 128
.
A Nucleophilic Reactions: Aqueous Systems ........ 128
.
B Nucleophilic Reactions: Nonaqueous Systems . . . . . . 131
.
C Reactions With Unsaturated Compounds . . . . . . . . . . 133
.
D Reactions With Aliphatics . . . . . . . . . . . . . . . . . . . 141
.
VII REACTIONS O F UNSATURATED NITROGEN
COMPOUNDS ............................. 142
.
A Nitric Oxide ............................ 142
.
B Azo Compounds .......................... 143
VIII . CONCLUSION ............................. 143
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 144
73
74 ERIC W. STERN
I. INTRODUCTION
-
C,H, + +02 CH,CHO 14)
Olefins react with water and salts of Pd(1I) to form carbonyl com-
pounds having the same carbon skeleton a s the original olefin [Eq.
( 5 ) ] . Thus the reaction which results in the conversion of ethylene to
TABLE 1
Reaction of Monoolefins with Pd(I1) in Aqueous Systems
Conditions -
Olefin Catalyst Temp.,"C Time, min Product Yield, % Ref.
?(, Propionaldehyde in
Solution composition, moles/liter ketone/aldehyde mixture
crease the olefin-metal double bonding and increase the overall polar-
ization of the olefin, leading to loss of selectivity with respect to ke-
tone. Anions which a r e poor ligands should have little or no effect,
as is shown in the case of fluoride. The apparent lack of difference
between sulfate, a poor ligand, and chloride might be explained on
the basis that ligand exchange with solvent water occurs to some ex-
tent during the reaction and that product distributions reflect the for-
mation of some common reactive species containing aquo or hydroxo
ligands. This exchange is depressed when excess ligand is present,
but to a greater extent with chloride than with bromide.
The effect of added acids is twofold. In experiments with HClO, it
was shown [3] that the aldehyde/ketone product ratio from propylene
varied inversely with the pH of the solution. In the case of addition
of increasing amounts of HC1, the effect was somewhat more pro-
nounced, apparently due both to decreasing pH and increasing chloride
concentration (see below). The effect of other acids is summarized
in Table 3 . A s can be seen, aldehyde production is a function of acid
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strength (pH effect) and the ability of the anion to complex with Pd(I1).
TABLE 3
Reaction of Propylene with Aqueous 0.05 M K,PdCl, at 70"
in the P r e s e n c e of Various Acids
TABLE 4
Effect of Olefin Structure on Rate of Reaction with Aqueous PdC1;' at 25"
~ ~~ ~~
k (M'/sec x lo5),
K. olefin complex complex Olefin
Olefin formation decomposition solubility, mM Ref.
Activation a a r a m c t e r s
AH *, Temp. range,
Olefin kcal/mole AS*,eu "C Ref.
halides, inhibition decreasing in the order, I- > Br- > C1- [9]. This i s
in accord with the nucleophilic activity of these ions in displacement
reactions in planar Pd(I1) complexes [231. With chloride the inhibiting
effect on rate has been shown to be generally of second o r d e r f o r the
reaction of ethylene [12,21,29], propylene [14,20], the butenes [14],
and cyclohexene [7] in the concentration ranges studied. At low chlo-
ride ion concentrations, however, the r a t e s of reaction of ethylene,
propylene, and 1-butene are first o r d e r with respect to chloride 1271
passing through a maximum and then decreasing a s reported pre-
viously. A change in the r a t e law to second-order dependence on
PdC1, when no additional chloride is present has also been reported
[261.
Other salts which a r e not good complexing agents, such a s phos-
phates, fluorides, nitrates, and sulfates, show less effect but, in gen-
e r a l , do inhibit the reaction with increasing concentration. In some
cases, such a s with phosphates and iodides, some of the inhibiting
effect is due to formation of insoluble Pd(I1) species [S].
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- d(olefin)/dt = k(PdX,)(olefin)/(X-)'(H")
r = a(H+)(Cl-)/b + (H')2(Cl-)3
3 . Mechanism
C,H, f H,O __
PdC12+CzH,0H - CH,CHO + Pd + 2HCl (8)
tion products, even when the reaction is carried out on a large scale
[3]. From this it must be concluded that alcohol, if it is formed a s an
intermediate, must react with extreme rapidity. However, it has been
shown that the oxidation of olefins to aldehydes and ketones is much
faster than the corresponding reaction of alcohols [ 3,311. Therefore,
the reaction of olefins and water does not proceed via alcoholic inter-
mediates. Similar results were obtained previously in the reaction
of the ethylene-PtC1, complex [ 321 for which this mechanistic route
had been suggested [ 331.
Another possibility considered by early workers in the field [ 341
was the formation of vinyl alcohol as the actual reaction product. The
reaction was pictured as proceeding a s in Eq. (9).
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The conclusion that this mechanistic scheme was valid was bolstered
by the isolation of vinyl substituted products when other nucleophiles
were substituted for water in nonaqueous media [34,35]. However, if
vinyl alcohol were indeed produced in the reaction, the acetaldehyde
formed when the reaction is carried out in D,O should contain one
deuterium. That it does not 191 indicates that acetaldehyde is formed
directly and that all four hydrogens in the product come from ethyl-
ene. This result also eliminates Pd-H elimination from the inter-
mediate.
Broadly speaking, the mechanism of reaction consists of two steps:
formation of an olefin-Pd(I1) complex and decomposition of the com-
plex leading t o aldehydes and/or ketones. Separation of these steps
has already been mentioned. Efforts have also been made to obtain
direct evidence for olefin complex formation and to determine the
nature of the complexes formed. These have centered around attempts
to isolate complexes under conditions which inhibit their decomposi-
tion. For example, when ethylene was reacted with PdC1, in D,O,
complex formation was observed visually, but isolation was not
achieved [9]. Likewise, inhibition of reaction at high acid concentra-
tion also led to some complex precipitation, but, again, no isolation
PI.
On the other hand, unreactive olefins such as isobutylene, methyl-
cyclohexene, and substituted styrenes yielded isolatable complexes
from 50% acetic acid solution [S]. These materials were identical to
UNSATURATED LIGANDS IN Pd(I1) COMPLEXES 85
hydroxoolefin complex, (5), and these steps account for the additional
rate enhancement by C1' and H a s well a s the consequent additional
inhibition by these ions. The assumption of a cis-hydroxoolefin com-
+ CH,CHO
.-[
(HO-~CH,CH,)PdCl,]- * T-((HO-CH=CH,)P~HC~,]- (19)
p H 2
o-[(CH,-CHOH)PdCl,]- + H,O CH,-CH
‘OH
+ (PdCl,),- (21)
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CH,-CH
/OH,
‘OH
- CH,CHO + H,O+
This route avoids the difficulty of the observed lack of isotope ex-
change since the latter is consistent with direct 1,2-hydride shifts in
organic rearrangements [46]. However, although it is known that
zerovalent platinum is capable of forming hydrides with acids, this
reaction has not been demonstrated f o r palladium [ 471. Moreover,
this route has the disadvantage of not being directly applicable to the
reactions of olefin-Pd(I1) complexes in nonaqueous media.
A view which s k i r t s the various difficulties associated with the
above mechanisms [ 121 suggests that outright palladium hydride for-
mation does not occur, but that palladium assists in the transfer of
hydride from the hydroxyl carbon to the carbon which originally was
a-bonded to palladium [Eq. (25)].
H H
H I
‘C,-C-0---H
I - CH,CHO + HC1 + Pd
II ’\ Ii
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-\,
Pd--- H
c1’
This suggestion is coupled with the proposal that the formation of the
oxypalladation intermediate [Eq. (16)] is the rate-determining step in
the sequence. The reasoning behind this choice is that, since no kin-
etic isotope effect was observed for the reactions of C,D,and C,H,,
C-H bond rupture, i.e., the hydride shift, cannot occur in the rate-
determining step. Step (16), as the only nonequilibrium step prior to
the hydride shift, i s therefore chosen a s being rate determining. How-
e v e r , lack of isotope effect in this instance can also be explained via
the sequence of Eqs. (19)-(22) in which the hydride shift is accom-
plished prior to the rate-determining hydrolysis in a series of r e a r -
rangement equilibria requiring little reorganization energy.
When nucleophiles other than water react with olefins and Pd(I1)
salts, unsaturated products are formed which a r e , in many cases,
vinyl compounds. The reaction has been established for carboxylic
acids and their salts[34,35], alcohols [34,35], amines and amides [35],
cyanides [49], and carbanions [50]. Palladium(I1) is reduced to pal-
ladium(0) in these c a s e s , but, again, can be regenerated in situ by a
variety of oxidizing agents [34,51,52]. Therefore, in effect, it is pos-
sible to consider these reactions a s palladium catalyzed.
In t e r m s of product distributions the reaction of olefins with nu-
cleophiles in nonaqueous media is f a r more complex than the c o r r e -
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TABLE 6
TABLE 6 (continued)
1. E s t e r Formation
vinyl acetate [Eq. ( 2 6 ) ] , ester formation has been studied more ex-
tensively than other nonaqueous nucleophilic reactions.
ing from 40yG in glacial acetic acid to 1%at 25% acetic acid in di-
methyl acetamide [ 641. Solvents less effective in reducing diacetate
yields were sulfones, nitriles, ketones, and e s t e r s [64J. No diacetate
formation was observed with low concentrations of acetic acid in hy-
drocarbon [24,35] and ether 1221 solvents, in vapor phase at low ace-
tic acid concentrations relative to olefin [22], o r when t h e reaction
was c a r r i e d out with lithium acetate but without added acetic acid
(641.
Solvent effects have also been noted with respect to product dis-
tributions among unsaturated e s t e r s . For example, the amount of
cis- and trans-n-propenyl acetates produced relative to isopropenyl
acetate in the reaction of propylene with acetic acid is increased by
a factor of 2 in going from isooctane to 1,2-dimethoxyethane solvent,
under otherwise identical conditions [221. A similar effect has been
noted on adding benzonitrile or dimethyl sulfoxide to an acetic acid
medium, the amount of primary e s t e r increasing by a factor of 2 in
the former and 4 in the latter for the reaction of 1-octene [53]. Di-
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Evidence has been adduced supporting the latter course. When the reac-
tion of ethylenewas carriedout in CH,COOD, the ethylidene diacetate pro-
duced contained no deuterium [65], a result not possible if diacetate
formation proceeded as in Eq (27). The observation that high-boiling
products (diesters) a r e greatly increased a t short reaction times in
the reaction of 1-hexene [60] supports this view. The enhanced ability
of acid amides, sulfonamides, and sulfoxides to suppress diacetate
formation has been explained on the basis of decreased acetic acid
activity due to hydrogen bonding to solvent in these cases [64].
The influence of solvent on the position of esterification is more
difficult to explain. This effect is generally noted for donor solvents
94 ERIC W. STERN
tion between ethylene and acetic acid will occur without added ace-
tate in N,N-dimethylacetamide [64] o r in glacial acetic acid a t ele-
vated temperatures and pressures [ 691. Conversely, the reaction can
also be carried out with acetate alone [64]. Addition of acetate to
systems containing acetic acid increases the reaction rate [64]. A
quantitative studyofthis effect, in the reaction of PdC1, with C,H,
and HOAc 170], shows an increasing rate a s a function of acetate con-
centration at low acetate concentrations and a decreasing rate at
higher concentrations, the position of the maximum being somewhat
dependent on the PdCl, concentration in the medium but independent
of the acetic acid concentration o r the ethylene partial pressure. The
decrease in rate at higher concentrations is too large to be explained
on the basis of decreasing ethylene solubility resulting from increas-
ing acetate concentration [70].
A s expected, the rate of reaction increases with temperature (Ta-
ble 7). However, it is clear that the magnitude of the effect depends
TABLE 7
Effect of Temperature on Rate of Ester Formation
Activation parameters
AH*, Temp. range,
Olefin System kcal/mole AS*, eu "C Ref.
C2H4 PdCl,, NaOAc, HOAc, 35 < 50" [701
p-benzoquinone 8.9 > 50"
C2H4 Pd(OAC)2, HOAC, 16.6 -10.7 19-48 "711
p-benzoquinone
-- - - - - ~-- I
UNSATURATED LIGANDS IN Pd(I1) COMPLEXES 97
TABLE 8
Deuterium Isotope Effects in Ester Formation from Propylene
Propene Propene-2-d
~- ~
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(absence of added acetate) [64], but n-olefin complexes yield the same
products observed when olefins and Pd(I1) s a l t s a r e added separately
to reaction systems [34,35,64]. On the other hand, it has been shown
that n-ally1 palladium(I1) complexes, which can form from olefins
higher than ethylene, do not react at comparable r a t e s o r yield the
s a m e products a s those formed in reactions of the parent olefins
158,621. Moreover, the observed difference in products from 1- and
2-olefins could not be explained on the basis of n-ally1 complex in-
termediacy since the same n-ally1 complex would be formed from
both isomers of the s a m e olefin [39,58]. Although n-ally1 complex
formation has been observed in s e v e r a l instances [55,60], particularly
when reactions were c a r r i e d out at elevated temperatures [SO], these
materials were shown to be by-products.
In systems containing PdC1, solubilized with excess chloride, for-
mation of the n-complex of ethylene is expected to occur by the same
equilibrium reaction a s in aqueous system [Eq. (ll)],followed by
nucleophilic attack on the complex either by acetate [Eq. (28)] o r by
acetic acid [Eq. (29)]. In the latter c a s e , a s with water, proton re-
moval must follow, and this can be assisted by either acetate or a
basic solvent [64] [Eq. (30)].
[ P ~ C ~ , ( O A C ) ,+
] ~C,H,
- == [C,H,PdCl,(OAc)]- + OAc-
[ C,H,PdCl,(OAc)]- =+ [AcO-CH,CH,-P~C~,]-
(8)
Again, it has not been possible to prepare such intermediates from
simple olefins. However, reaction of 2-chloromercuriethyl acetate
with palladium chloride in ether has been found to lead, at least par-
tially, to reduction of palladium and formation of vinyl acetate 1381.
The intermediacy of (8) formed by metal exchange therefore has been
assumed. A similar assumption has been made in the reaction of 2-
chloromercuriethyl acetate with PdC1, and NaOAc in glacial acetatic
acid which yielded vinyl acetate and ethylidine diacetate. However,
under the conditions employed, deoxymercuration followed by olefin-
PdC1, reaction was not precluded.
Also, as in the case of aqueous reaction, analogies have been drawn
to similar reactions of Tl(II1) and Hg(I1) [38,39], which are known to
proceed via oxymetallation. In the case of Tl(III), reaction with cyclo-
hexene in glacial acetic acid [61,72] leads to extensive ring contrac-
tion and 1,2-diacetate formation. Mercuric acetate, on the other hand,
yielded allylic acetate [61]. However, in contrast to reactions involv-
ing palladium, allylic products from Hg(OAc), reaction with linear
olefins were the same for both 1- and 2-olefins [58,60]. In moist
acetic acid, mercuric acetate reacts with cyclohexene to give 1,2-
glycols and ring-contracted products [ 611.
Stable oxypalladation products are formed by reaction of certain
cyclic diolefins, Pd(I1) s a l t s , and alcohols in the presence of a weak
base [42]. These materials have been investigated in some detail
UNSATURATED LIGANDS IN Pd(I1) COMPLEXES 101
([73] and references therein). It has been shown that the alkoxyl and
palladium moieties are located trans to each other with the palladium
endo and the alkoxyl exo in systems such as dicyclopentadiene, (9))
and that their formation is readily reversed by acid. Because of this,
it has been suggested that they are formed by nucleophilic attack of
alcohol (from the bulk solution) on the n-diolefin complex, the base
aiding in removal of the hydroxyl hydrogen simultaneously with, o r
subsequent to, addition. The same stereochemistry (addition of nu-
cleophile exo to metal) is found in reaction of (n-cyclopentadieny1)-
(n-tetraphenylcyclobutadiene) palladium bromide [ 741.
If oxypalladation does indeed occur) the stereochemistry of the
insertion might be expected to influence product distribution, partic-
ularly in reactions of cyclic olefins. The suggestion has been made
[62] that the products from reaction of cyclohexene with PdC1, and
NaOAc in glacial acetic acid, which are cyclohexen-3-yl and cyclo-
hexene-4-yl acetates but not the expected enol ester, can be explained
by assuming equatorial-axial (cis) oxypalladation followed by palla-
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(9)
x\ Pd--CH,-CH-OAc
X
’
q CH\
- CH,&H-OAc
(11)
+ PdX- + X- (33)
H&-CH-
,\ II
OAC - CH,CH,-~H-OA~
(34)
CH3
Decomposition of (8) by attack of acetate on the palladium-carbon
bond of (8) o r , in the case of higher olefins, on isomerized oxypalla-
dation products in which palladium has migrated down the chain [39]
is successful in explaining 1,2- and 1,3-products obtained from the
butenes in the presence of copper, but again fails in explaining the
absence of these products in copper-free systems.
Again, these difficulties inherent in two-carbon insertion mecha-
nisms a r e overcome by assuming a one-carbon insertion. Suggestions
concerning rearrangement of initially formed 1,Z-insertion to 1,l-in-
sertion products have already been discussed in connection with the
reaction in aqueous medium. A mechanism involving direct conver-
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Few of the suggested mechanisms have taken into account the var-
ious factors affecting product distribution. For example, since diace-
tate formation has been shown to be a function of the acetic acid con-
centration, diacetate formation must be due to acetic acid attack on a
carbonium ion or Pd-C bond in the final step. Acetate, on the other
hand, is a strong base in acetic acid and may well assist in the final
proton removal. Since it appears that the initial nucleophilic attack
can be either by acetate o r by acetic acid, the question is raised a s
to why acetate acts as a nucleophile only once in the reaction. P e r -
haps these observations constitute evidence that acetate incorpora-
tion into the complex before attack is essential.
Solvent and salt influences on product distributions a r e also largely
not a part of mechanistic suggestions. A possibility not yet considered
is that the addition of donor molecules (solvents or salts) aids in the
rearrangement of T - to a-complexes by stabilizing the latter. Involve-
ment of donor molecules in n-ally1 to u-ally1 palladium complexes
has been described [76]. Stabilization of a u-complex, if formed, may
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H L
F
-< c1
/ \
H H
As indicated in Eq. (36), nucleophilic attack can -e launchec ?om
either above o r below the plane and, therefore, can occur on either
end of the double bond, leading, in the case of propylene, to I- o r 2-
substitution. The hydride shift can be pictured a s occurring simulta-
neously to give a 1-carbon insertion product, or an oxypalladation prod-
uct can be formed. An advantage of the former view, in addition to
more readily explaining the lack of 1,2-disubstitution, is that, if donor
molecules occupy all available coordination sites, formation of the
a-bond with the terminal carbon would be less hindered, thus account-
ing for the enhancement of attack on that position in the presence of
donor solvents and excess acetate or chloride. Moreover, the in-
creasing rate of terminal substitution with time in a nonregenerated
106 ERIC W. STERN
ularly well disposed for interaction with the axial position, and this
may be the preferred decomposition route leading to such products.
Increase of the electron density on palladium by the presence of do-
nor solvents would increase both the tendency f o r pentacoordination
and proton affinity and, therefore, could explain the enhancement of
allylic substitution in the presence of such materials.
Admittedly, the above mechanism has the same drawbacks as the
previously discussed 1-carbon insertion. Further work in this a r e a
is necessary to determine which of the suggestions enumerated above
have validity and to what extent current mechanistic thinking may
need further modification.
2 . Ether Forination
Ethylene reacts with alcohols and PdC1, to yield vinyl ethers and
acetals [Eq. (39)]. Recovery of acetal from alcoholic media [34]and
of acetal and trace amounts of ether from alcoholic media containing
sodium alcoholate [38]hasbeen reported. On the other hand, either
UNSATURATED LIGANDS IN Pd(I1) COMPLEXES 107
4. Nitriles
5. Carbanions
C. Double-Bond Isomerization
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\ ' (40)
,y,- ' 'PdH
I /Pf\
o r an intermolecular hydride transfer in an addition-elimination of a
palladium hydride species [Eq. (4 1)).
R-CH,CH
= CH, * RCH,-CH-CH,
Pd-H
/ I
I
'I
I
Pd ,
=+ RCH
'I
Pd-H
+ CH-CH,
(41)
* RCD
+= RCD,-CH-CH,
I
-Pd-
T
-Pd-D
CH-CH,
I
I
I
41
* RCD-CHD-CH,
R-CD
T
-Pd-H
CD-CH,
-Pd-
I
I
Since palladium deuteride species also a r i s e in the course of this s e -
quence, the isotope effect is also assumed to control further scatter-
ing of deuterium to terminal carbon 186,911 [Eq. (43)j.
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+ R-CH2-CH=CH,,
-CD+ CD-CH, . R-cD,-
.CH+ CH,
-pP-D
I
I
-R-CD=CD-CH,
1I
* R-CD,-CD
RCD,-CD-CH,
-Pd-
I ?=
-Pd-H
CH, e=R-CD,-CHD-CH,
I
-Pd-
I I '(43)
D. Condensation Reactions
tion, the reaction being both faster and m o r e selective in benzene than
in dioxane. Further investigation showed that the C,H,-PdC1, complex
catalyzed the formation of butene from ethylene a t 25" and atmospher-
ic p r e s s u r e . This reaction can also be c a r r i e d out in the absence of
preformed complex, but only under more severe conditions [97].
Somewhat different olefin dimerizations which have been reported in
the presence of PdC1, a r e 1,l-diphenylethylene to 1,1,4,4-tetraphenyl-
butadiene and 2-methylstyrene to 2,5-diphenyl-2,4-hexadiene[ 61.
Cyclic olefins and diolefins yield polymers. Thus norbornene and
various substituted norbornenes are polymerized in the presence of
PdC1, to low molecular weight polymers, the polymer structure de-
pending on the presence and nature of functional groups on the nor-
bornene nucleus [ 981. Norbornadiene exclusively yields 1,2-polymer
[98], whereas butadiene yields a mixture of 1,2 and trans-1,4 poly-
m e r in which the former predominates [99].
A result of particular interest has been obtained in the polymeri-
zation of butadiene in which it was shown that the polymer structure
was extremely sensitive to the nature of the palladium(I1) catalyst
employed [loo]. It was found that with PdCl, 83% of the polymer had
the 1,2-structure, the remainder being of the trans- 1,4 configuration.
The use of salts of PdC1:- and PdC12,- increased the proportion of 1,
2-polymer to 98%. Similarly, PdBr, yielded 91% 1,2-polymer. On the
other hand, PdI, yielded 85% of the t r a n s 1,4-materials and Pd(CN),
yielded 78%, whereas PdSO, and Pd(NO,), yielded noncrystalline low
molecular weight materials. The addition of various neutral ligands
also influenced the reaction. Addition of dimethyl sulfoxide and t r i -
phenyl- and tributylphosphines slowed the reaction and triethyl phos-
114 ERIC W. STERN
2CHZ=CH-CH=CH, + B(C,H,CN),PdCl, -.
CH,C1
I
CH,C1
(14)
R’
,
CHR‘
CH/’
H I
-9 \fl
Pd-bcH
CH
--+
(47)
I
R R
R’-CH=CH-CH-CHR + Pd(0)
Rx, 80
C
.CH, I
+ C-CH, + Pd
I’
CH
‘R’ I
R’
F. Hydrogenation
? ? rp
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tion state of the metal is therefore intermediate between zero and +2.
Both complexes a r e unstable. In the absence of air the barium salt
of the acetylide shows somewhat greater stability. However, it is
readily decomposed by water, dilute acids, and most organic solvents
with the formation of unidentified colored organic materials. Reduc-
tion of the Pd(I1) acetylide to a Pd(0) acetylide by potassium in liquid
ammonia has been c a r r i e d out [133]. The resulting compounds are
l e s s stable and decompose explosively.
It is likely that complexes of either type represent a primary stage
in the formation of oligomers and polymers from acetylenes. How-
e v e r , data available at this time are insufficient to warrant detailed
speculation. In the case of cocatalysis by metal hydrides, t r a c e r ex-
periments indicate product deuteration and palladium hydride addition
to acetylene as a primary step has therefore been proposed [131].
d(biphenyl)/dt = k,(PdCl,)(C,H,)
o+
'\ NaOAc
PdC1,
- @ P d C l +NaCl + HOAc (51)
+ OAC--*
PdC1,
H
1. Aqueous Systems
TABLE 9
Reactions of a,P-Unsaturated Compounds With Aqueous Pd(I1)
Reagent Product
Butadiene Crotonaldehyde
Crotonaldehyde Triacetylbenzene
Acrylic acid Acetaldehyde
Crotonic acid Acetone
a-methyl acrylamide Propionaldehyde
Crotonamide Acetone
Acrylonitrile P -Cyanoacetaldehyde
Nitroethylene Nitroacetaldehyde
1-Nitro-1-propene Nitroacetone
2 . Nonaqueous Systems
R-CH=CH,X + HY CH,-Y
PdC1,+~-~~= + HX (53)
in excess of the amount of Pd(I1) employed can be obtained in the ab-
sence of oxygen and regenerating agents [22]. An interesting facet of
the reaction in nonaqueous media is that 1-halo- 1-olefins yield l-sub-
stitution products only. Thus the only product of reaction of l-bromo-
1-propene with acetic acid in di(2-methoxyethyl) ether was l-acetoxy-
1-propene [22]. This result contrasts sharply with the PdCl, catalyzed
hydrolysis of the same compound which leads to acetone formation
with greater than 90% selectivity [ 1391. As in aqueous systems, 2-
halo-1-olefins form 2-substituted products [22].
The high reactivity of the monohaloolefins in the presence of Pd-
(11) salts is somewhat surprising in view of the demonstrated inert-
ness of such materials in displacement reactions [142]. A priori as-
sumption of 7i-complex formation between the haloolefin and Pd(I1)
appears justified in view of the similarity in kinetic pattern to olefin
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H\h/
" II O n
-c-/o'I
I1
,l
PdClF
1. Aqueous Systems
2. Nonaqueous Systems
Br > C1> NO, > I > SCN NH, > Thio > CN-
This r a t e dependence is in r e v e r s e order of the stability of the com-
plex s a l t s except for bromide and chloride. The greater activity of
the bromide was interpreted a s being due to its greater rate of aqua-
tion.
Reaction of Pd(I1) salts with CO is inhibited by increased common
anion concentrations 1150- 1531, presumably, a s in olefin reactions,
by interference with complex forming equilibria. The reaction is
a l s o inhibited by large concentrations of acid, although, in systems
regenerated by p-benzoquinone, small amounts of acid have an ac-
celerating effect [ 1541. Addition of bases such as acetate and par-
ticularly KOH greatly accelerate the rate [ 1511.
The effectiveness of a number of inorganic and organic oxidizing
agents in maintaining palladium in the +2 oxidation state during CO
oxidation has been demonstrated. These a r e salts of Cu(I1) and
Fe(III), CrCl,, K.$r207, H202 11521, and quinones [154,155]. Com-
parison of reaction r a t e s with and without p-benzoquinone showed
enhancement by a factor g r e a t e r than two in the presence of quinone
11561. Metal precipitation was not observed when the quinone was
UNSATURATED LIGANDS IN Pd(I1) COMPLEXES 129
used [ 155,1561, and this has been interpreted as indicating that the
palladium atom acts as a bridge for electron transfer between CO
and the oxidizing agent [156]. This assumption is supported, in part,
by a calculated entropy of activation, S* = -22.4 eu, which i s in sub-
stantial agreement with reactions in which electron transfer between
metal ions is facilitated by ligand bridging. In the presence of
quinones whose redox potential is below that of the Pd(I1)-Pd(0)
system, palladium precipitates or remains in solution as complexed
Pd(0) [155]. In these systems electron transfer is incomplete, and
the quinone aids the transport of electrons to metal only [ 1561.
Formation of carbonyl complexes a s intermediates in the reac-
tion of aqueous Pd(I1) salt solutions with CO is indicated by the re-
action of stable carbonyls with water. Thus the monocarbonyl com-
plex, [Pd(CO)Cl,], [ 1571, reacts with water to f o r m CO, and Pd 11491
[Eq. W ) ] .
(21)
Br
[Pd(CO)Br,(OH)]- + CO -
Br
+ H,O - PdCO + CO, + 2Br- + H,O+ (72)
O H
-
-H+ \ /
I1
C-N-R
I
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/pd\
co
2
Pd
'co
0
c
Pd + H'
' 'coPd (77)
(24)
(23)
Support for at least transitory formation of a palladium hydride,
possibly stabilized by carbonyl, has been obtained by the appear-
ance of a band a t 2130 cm-l in the infrared spectra of reaction mix-
t u r e s , which grew in intensity a t about the same rate a s the isocy-
anate band at 2270 cm'l [22]. Although this band could be due to a
carbonyl complex, the observed frequency is well above that of the
known Pd carbonyl chlorides and that of a complex containing amine
and CO [ 1571.
An interesting application of the reaction of CO with nucleophiles
and Pd(I1) salts is the preparation of n-ally1 complexes. It was found
UNSATURATED LIGANDS IN Pd(I1) COMPLEXES 133
CH,-
Cl, ,,CH
pd ~IYCH+ CO, + HCI
TH,
1. Olefins
The reaction can also be c a r r i e d out with the olefins and PdC1, added
separately to the reaction mixtures. It is rapid a t room tempera-
t u r e in benzene and, when starting with the preformed complexes,
is accompanied by extensive decomposition. Product yields, which
a r e generally not high, decrease with increasing chain length of n-
1-olefin, a r e lower for internal olefins than those from the c o r r e s -
ponding terminal olefins, and a r e further reduced when the olefin
is t r a n s . Branching on the double bond of a terminal olefin has
about the same effect on yield as moving the double bond to the 2-
position, The yield from isobutene is about the same as from cis-
2-butene. Cyclic olefins yield mixtures of c i s and trans-p-chloro-
acyl chlorides in which the latter predominates. However, large
134 ERIC W. STERN
R-CH=CH, + PdC1, + CO -.
H
I
Pd(C0)X + R-C-CH,COCl
I
c1
Steric factors in the transition state a r e presumed to direct the
chloride to attack at C-2 in all c a s e s . Since acyl halides a r e con-
UNSATURATED LIGANDS IN Pd(I1) COMPLEXES 135
2. Allylic Compounds
CH,=CH-CH,-COCl + Pd(CO),
Since the reaction is catalytic, the metal o r Pd(0) carbonyl must re-
act with more allyl compound to regenerate the active species as
has been demonstrated for Pd and allyl bromide [ 1851.
UNSATURATED LIGANDS IN Pd(I1) COMPLEXES 137
3. Diolefins
),PdIq
CH,=CH-CH,-CH,-CH=CH, + CO (BusP
MeOH
CH,COOMe
(85)
CO, MeOH
CH,COOMe C H,Pd(L, )X
UNSATURATED LIGANDS IN Pd(I1) COMPLEXES 139
4. Allene
5. Acetylenes
Reaction of acetylenes with CO results in products that reflect
the ability of the palladium catalysts to promote both mono- and
multicarbonylation of unsaturated compounds and coupling of ace-
tylenes. The particular products obtained are frequently a function
of reaction conditions. In most cases it is unclear whether palla-
dium metal or palladium(I1) i s the catalyst. However, results a r e
usually somewhat better when palladium is added a s Pd(II), and the
140 ERIC W. STERN
H\C/coC1
+ II
/c,
COCl H
1. Palladium Alkyk
2 . Cyclopropane
A. Nitric Oxide
B. Azo Compounds
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@-N=N-@ + PdC1, -
VIII. CONCLUSION
Acknowledgement
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