Cis/trans isomerization of phosphinesulfonate palladium(II) complexes

Article abstract of DOI:10.1002/anie.201100065

(Chemical Equation Presented) With a little help from a friend: Chain growth in olefin polymerization by [{PO}PdR] catalysts is believed to occur by unimolecular cis-P,R- to trans-P,R-[{PO}PdR(olefin)] isomerization, with subsequent insertion. Studies with [{PO}Pd(py)₂]⁺ (py=pyridine) and non-equilibrium cis/trans mixtures of [{PO}PdClP(O-o-tolyl) ₃] indicate that an external ligand is necessary for cis/trans isomerization of {PO}Pd complexes (see scheme). {PO}=2-Phosphinosulfonate.

Full text of DOI:10.1002/anie.201100065

Communications
DOI: 10.1002/anie.201100065
Homogeneous Catalysis
cis/trans Isomerization of Phosphinesulfonate Palladium(II)
Complexes**
Matthew P. Conley and Richard F. Jordan*
The copolymerization of ethylene with polar vinyl monomers
by insertion processes enables the direct synthesis of func-
tionalized plastics.[1] [{2-phosphinoarenesulfonate}PdR] spe-
cies ([{PO}PdR]) copolymerize ethylene with a wide range of
polar monomers to linear copolymers.[2] The {POÀ} ligand
incorporates strong-trans-influence phosphine and weak-
trans-influence sulfonate ligands in a cis arrangement in the
{PO}Pd complex.[3] Owing to this “electronic asymmetry,” the
two open coordination sites of a {PO}PdII unit are quite
different, which may contribute to the reactivity of these
catalysts.
trans-P,R-1 are in fast equilibrium and that chain growth
occurs by insertion of trans-P,R-1. The cis-P,R-1/trans-P,R-1
isomerization was proposed to proceed via transition state
TS-A,[4b] in which the geometry at palladium center may be
described as square-pyramidal with one basal vacancy, or TS-
B,[4a] in which a terminal sulfonate oxygen atom coordinates
to palladium to form a five-coordinate species that undergoes
Berry pseudorotation. It has not yet been possible to observe
the isomerization of a cis-P,R-[{PO}PdR(L)] species to the
trans-P,R isomer. Therefore, we have examined two model
{PO}PdII systems to probe how cis/trans isomerization occurs.
We first prepared [{PO-OMe}Pd(py)2]+ [3, {PO-OMe} =
2-P(o-MeOC6H4)2-p-toluenesulfonate, py = pyridine, Eq. (1)]
Two isomers and insertion (i.e., chain-growth) modes are
possible for [{PO}PdR(ethylene)] complexes (1), as shown in
Scheme 1. The species cis-P,R-1 is more stable than trans-P,R-
1 owing to the unfavorable trans arrangement of the strong-
and investigated the mechanism of exchange of the pyridine
ligands between the sites cis and trans to the phosphorus
donor (cis-P and trans-P, respectively). Complex 3 was
prepared by the reaction of [{PO-OMe}PdCl(py)][5] with
Ag[SbF6] in the presence of pyridine and characterized by
NMR spectroscopy, ESI-MS, elemental analysis, and X-ray
diffraction.[6]
Scheme 1. Proposed chain-growth mechanism for [{PO}PdR] catalysts.
Crystallization of
3
from pyridine yields [{k1-PO-
OMe}Pd(py)3][SbF6] (4). X-ray analysis of 4 shows that the
Pd center is bound by three pyridine ligands and the
phosphine moiety of the {PO-OMe} ligand in a square-
planar arrangement (Figure 1). The distance from the Pd
atom to the nearest sulfonate oxygen atom (O(3)) is
3.066(5) ꢀ, which is near the sum of the van der Waals radii
of Pd and O (3.12 ꢀ). These results show that the sulfonate
has been nearly completely displaced by pyridine. NMR
spectroscopy studies showed that 4 is in equilibrium with 3
and free pyridine in CD2Cl2 (Keq = [4][3]À1[py]À1 = 0.28mÀ1 at
208C).
trans-influence alkyl and phosphine ligands in the latter
species. Migratory insertion of cis-P,R-1 is expected to yield
À
trans-P,R-2, in which the Pd C bond is trans to the phosphine
ligand, while insertion of trans-P,R-1 is expected to yield cis-
À
P,R-2, in which the Pd C bond is cis to the phosphine ligand.
DFT studies predict that the barrier to ethylene insertion of
cis-P,R-1 is approximately 11 kcalmolÀ1 higher than that of
trans-P,R-1.[4] The calculations also suggest that cis-P,R-1 and
[*] Dr. M. P. Conley, Prof. Dr. R. F. Jordan
Department of Chemistry, The University of Chicago
Chicago, IL 60637 (USA)
The intra- and intermolecular pyridine exchange proper-
1
ties of 3 were probed by NMR spectroscopy. The H NMR
spectrum of 3 in CD2Cl2 at 208C contains sharp trans-P
pyridine and cis-P pyridine signals in a 1:1 integral ratio. The
excess line widths of the trans-P and cis-P pyridine resonances
are below the detection limit (ca. 0.5 Hz), thus indicating that
intramolecular pyridine exchange does not occur on the
timescale of NMR spectroscopy (T2). The EXSY spectrum of
Fax: (+1)773-702-0805
E-mail: rfjordan@uchicago.edu
[**] This work was supported by the U.S. Department of Energy
(DE-FG-02-00ER15036).
Supporting information for this article is available on the WWW
under http://dx.doi.org/10.1002/anie.201100065.
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_
Scheme 2. Pyridine exchange mechanism for 3. PO={PO-OMe}.
system in which the cis-P,P and trans-P,P isomers can be both
observed and their interconversion directly probed.[6] This
work led to the discovery of [{PO-iPr}PdCl{P(O-o-tolyl)3}] (5,
{PO-iPr} = 2-PiPr2-p-toluenesulfonate), which has these prop-
erties.
Figure 1. Molecular structure of the cation of [{PO-OMe}Pd(py)3][SbF6]
(4). Hydrogen atoms except H(24) are omitted. Bond lengths [ꢀ]:
Pd(1)–N(1) 2.051(6), Pd(1)–N(2) 2.096(6), Pd(1)–N(3) 2.028(6),
Pd(1)–P(1) 2.291(1), Pd(1)–O(3) 3.066(5), Pd(1)–H(24) 2.83.
The reaction of [{PO-iPr}PdCl(py)] with P(O-o-tolyl)3 in
the presence of B(C6F5)3 affords a 1:9 mixture of cis-P,P-[{PO-
iPr}PdCl(P(O-o-tolyl)3)] [cis-P,P-5, Eq. (2)] and trans-P,P-
[{PO-iPr}PdCl(P(O-o-tolyl)3)] (trans-P,P-5) in 94% yield. No
3 (CD2Cl2, 208C) does not contain crosspeaks between
corresponding trans-P and cis-P pyridine resonances, thus
indicating that the exchange is slower than the EXSY
timescale. These results show that the barrier to intramolec-
ular pyridine exchange is above 20 kcalmolÀ1.[7]
In the presence of a low concentration of pyridine (9 mm)
at 208C, the trans-P pyridine resonances of 3 in the 1H NMR
spectrum are coalesced with the free pyridine signals,
consistent with fast intermolecular associative exchange of
the trans-P pyridine with free pyridine. In contrast, the cis-P
pyridine signals of 3 maintain their original chemical shifts
and display little line broadening under these conditions. As
the concentration of free pyridine is increased, moderate
broadening of the cis-P pyridine signals is observed, consis-
tent with slow associative exchange of the cis-P pyridine with
free pyridine. The difference in rates of exchange of the trans-
P and cis-P pyridine with free pyridine is expected, since
phosphines are better trans directors than sulfonates.[8]
In the presence of free pyridine, the variable-temperature
1H NMR spectra of 4 contain sharp resonances for coordi-
nated and free pyridine, and the EXSY spectra do not contain
crosspeaks between 4 and free pyridine. Therefore, 4 does not
play a role in the pyridine exchange of 3 and free pyridine.
These results are consistent with the mechanism of
pyridine exchange for 3 shown in Scheme 2. Trigonal-
bipyramidal intermediates are omitted from Scheme 2; a
more complete mechanism is given in the Supporting
Information. Complex 3 binds pyridine to form the unob-
served five-coordinate intermediate (or transition state) C,
leading to associative pyridine exchange. The formation of 4
also occurs through C.
change in the cis-P,P/trans-P,P-5 ratio is observed by 1H NMR
spectroscopy when CD2Cl2, [D8]THF, or [D6]acetone solu-
tions of cis-P,P/trans-P,P-5 are heated at 358C over two days.
In contrast, addition of P(O-o-tolyl)3 to a solution of cis-P,P/
trans-P,P-5 in CD2Cl2 at 358C results in clean conversion of
the initial 1:9 cis-P,P/trans-P,P-5 mixture to an equilibrium
1.4:1 cis-P,P/trans-P,P-5 mixture [Eq. (2)]. The 31P{1H} and
1H NMR spectra of cis-P,P/trans-P,P-5 in CD2Cl2 at 358C in
the presence of added P(O-o-tolyl)3 contain sharp resonances
for cis-P,P-5, trans-P,P-5, and free P(O-o-tolyl)3 but no
resonances for new species, thus indicating that exchange of
free and coordinated P(O-o-tolyl)3 is slow on the time scale of
NMR spectroscopy and that significant quantities of new
species are not formed. These results show that the barrier to
direct isomerization of cis-P,P/trans-P,P-5 is high but that this
isomerization is catalyzed by P(O-o-tolyl)3.
The cis-P,P-5/trans-P,P-5 isomerization in the presence of
P(O-o-tolyl)3 in CD2Cl2 obeys first-order approach-to-equi-
librium kinetics [Eq. (3)]. kobs is the sum of the forward (k1,
trans to cis) and reverse (kÀ1, cis to trans) rate constants, and
Complex 3 differs from [{PO}PdR(olefin)] complexes in
that it is cationic rather than neutral and contains identical
pyridine ligands instead of electronically different alkyl and
olefin ligands. [{PO}PdCl(PR3)] complexes are better models,
because they have a neutral charge and contain electronically
different chloride and phosphine ligands. We generated a
small library of [{PO}PdCl(PR3)] complexes to access a
K
eq = k1/kÀ1. A plot of kobs versus [P(O-o-tolyl)3] is linear
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These studies establish that the cis/trans isomerization of
inorganic {PO}Pd complexes proceeds through five-coordi-
nate intermediates and not by a unimolecular mechanism.[9]
Similar process may be important for [{PO}Pd(R)(ethylene)]
catalysts in the presence of excess monomer. However, the
presence of an alkyl ligand may open up isomerization
pathways that are not available to the inorganic systems
studied here.[10]
Received: January 5, 2011
Published online: March 16, 2011
Keywords: homogeneous catalysis · isomerization · palladium ·
.
polymerization
Figure 2. Plot of kobs (sÀ1) for approach to equilibrium of cis/trans-P,P-5
versus [P(O-o-tolyl)3] from three separate experiments. For [P(O-o-
tolyl)3]=5.6, 23, and 46 mm, the data points for the separate experi-
ments overlap.
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(Figure 2). These data establish that trans-P,P-5/cis-P,P-5
isomerization is first-order in palladium and P(O-o-tolyl)3.
The equilibration of the 1:9 cis-P,P/trans-P,P-5 mixture in
the presence of P(O-o-tolyl)3 (46 mm) is only slightly faster in
[D6]acetone (kobs = 1.4(1) ꢁ 10À5 sÀ1) than in CD2Cl2 (kobs
=
À
1.1(1) ꢁ 10À5 s ), thus suggesting that ionization of the Pd
Cl bond does not play a role in the isomerization of 5.
A plausible mechanism for P(O-o-tolyl)3-catalyzed cis-
P,P-/trans-P,P-5 isomerization is shown in Scheme 3. P(O-o-
tolyl)3 reacts with trans-P,P-5 to generate the five-coordinate
À1
[3] The trans influence is defined as weakening of the bond trans to
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[6] See the Supporting Information.
[7] The lower limit to kexch detectable by EXSY is 1/T1, where kexch is
the first order rate constant for exchange and T1 is the relaxation
time of the proton used for the determination of kexch. The T1
value of the ortho-pyridine hydrogen in 3 at 208C is 3.2 s, so
k
exch < 0.31 sÀ1. See: C. L. Perrin, T. J. Dwyer, Chem. Rev. 1990,
90, 935.
[8] For a CD2Cl2 solution of 3 (16 mm) in the presence of 9 mm
pyridine at 258C, ktrans = 30000mÀ1 sÀ1 and kcis = 160mÀ1 sÀ1
.
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Scheme 3. Proposed mechanism for the P(O-o-tolyl)3-catalyzed isomer-
ization of 5.
intermediate trans-P,P-D. This intermediate isomerizes by
Berry pseudorotation to cis-P,P-E and then dissociates P(O-
o-tolyl)3 to form cis-P,P-5. A complete mechanism with
trigonal-bipyramidal intermediates is shown in the Support-
ing Information.
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