Mechanistic studies of the palladium-catalyzed copolymerization of ethylene and α-olefins with methyl acrylate

Article abstract of DOI:10.1021/ja964144i

Mechanistic aspects of palladium-catalyzed insertion copolymerizations of ethylene and α-olefins with methyl acrylate to give high molar mass polymers are described. Complexes [{N@?N)Pd(CH₂)₃C(O)-OMe]BAr'₄ (2) or [(N@?N)Pd(CH₃)(L)]BAr'₄ (1: L = OEt₂; 3: L @? NCMe; 4: L @? NCAr') (N@?N @? ArN = C(R)-C(R) = NAr, e.g., Ar @? 2,6-C₆H₃(i-Pr)₂, R @? H (a), Me (b); Ar' @? 3,5-C₆H₃(CF₃)₂) with bulky substituted α-diimine ligands were used as catalyst precursors. The copolymers are highly branched, the acrylate comonomer being incorporated predominantly at the ends of branches as -CH₂CH₂C(O)OMe groups. The effects of reaction conditions and catalyst structure on the copolymerization reaction are rationalized. Low-temperature NMR studies show that migratory insertion in the η²-methyl acrylate (MA) complex [(N@?N)PdMe{H₂C = CHC(O)OMe}]⁺ (5) occurs to give initially the 2,1-insertion product [(N@?N)PdCH(CH₂CH₃)C (O)OMe]⁺ (6), which rearranges stepwise to yield 2 as the final product upon warming to -20°C. Activation parameters (ΔH@? = 12.1 ± 1.4 kcal/mol and ΔS@? = -14.1 ± 7.0 eu) were determined for the conversion of 5a to 6a. Rates of ethylene homopolymerization observed in preparative scale polymerizations (1.2 s^-1 at 25 °C, ΔG@? = 17.4 kcal/mol for 2b) correspond well with low-temperature NMR kinetic data for migratory insertion of ethylene in [(N@?N)Pd{(CH₂)(2n)Me}(H₂C = CH₂)]⁺. Relative binding affinities of olefins to the metal center were also studied. For [(N@?N)PdMe(H₂C = CH₂)]⁺ + MA @? 5a + H₂C = CH₂, K(eq)(-95°C = (1.0 ± 0.3) x 10^-6 was determined. Combination of the above studies provides a mechanistic model that agrees well with acrylate incorporations observed in copolymerization experiments. Data obtained for equilibria 2 + H₂C = CHR' @? [(N@?N)Pd{(CH₂)₃C(O)OMe}(H₂C = CHR')]⁺ (R' @? H, Me, (n)C₄H₉) shows that chelating coordination of the carbonyl group is favored over olefin coordination at room temperature. Formation of chelates analogous to 2 during the copolymerization is assumed to render the subsequent monomer insertion a turnover-limiting step.

Full text of DOI:10.1021/ja964144i

888
J. Am. Chem. Soc. 1998, 120, 888-899
Mechanistic Studies of the Palladium-Catalyzed Copolymerization of
Ethylene and R-Olefins with Methyl Acrylate
Stefan Mecking,† Lynda K. Johnson,†,‡ Lin Wang,‡ and Maurice Brookhart*,†
Contribution from the Department of Chemistry, UniVersity of North Carolina at Chapel Hill,
Chapel Hill, North Carolina 27599-3290, and DuPont Central Research and DeVelopment,
Wilmington, Delaware 19880-0328
ReceiVed December 2, 1996
Abstract: Mechanistic aspects of palladium-catalyzed insertion copolymerizations of ethylene and R-olefins
with methyl acrylate to give high molar mass polymers are described. Complexes [(N∧N)Pd(CH2)3C(O)-
OMe]BAr′4 (2) or [(N∧N)Pd(CH3)(L)]BAr′4 (1: L ) OEt2; 3: L t NCMe; 4: L t NCAr′) (N∧N ≡
ArNdC(R)-C(R)dNAr, e.g., Ar t 2,6-C6H3(i-Pr)2, R t H (a), Me (b); Ar′ t 3,5-C6H3(CF3)2) with bulky
substituted R-diimine ligands were used as catalyst precursors. The copolymers are highly branched, the acrylate
comonomer being incorporated predominantly at the ends of branches as -CH2CH2C(O)OMe groups. The
effects of reaction conditions and catalyst structure on the copolymerization reaction are rationalized. Low-
temperature NMR studies show that migratory insertion in the η2-methyl acrylate (MA) complex [(N∧N)-
PdMe{H2CdCHC(O)OMe}]+ (5) occurs to give initially the 2,1-insertion product [(N∧N)PdCH(CH2CH3)C-
(O)OMe]+ (6), which rearranges stepwise to yield 2 as the final product upon warming to -20 °C. Activation
parameters (∆Hq ) 12.1 ( 1.4 kcal/mol and ∆Sq ) -14.1 ( 7.0 eu) were determined for the conversion of
5a to 6a. Rates of ethylene homopolymerization observed in preparative-scale polymerizations (1.2 s-1 at 25
°C, ∆Gq ) 17.4 kcal/mol for 2b) correspond well with low-temperature NMR kinetic data for migratory
insertion of ethylene in [(N∧N)Pd{(CH2)2nMe}(H2CdCH2)]+. Relative binding affinities of olefins to the
metal center were also studied. For [(N∧N)PdMe(H2CdCH2)]+ + MA h 5a + H2CdCH2, Keq(-95 °C) )
(1.0 ( 0.3) × 10-6 was determined. Combination of the above studies provides a mechanistic model that
agrees well with acrylate incorporations observed in copolymerization experiments. Data obtained for equilibria
2 + H2CdCHR′′ h [(N∧N)Pd{(CH2)3C(O)OMe}(H2CdCHR′′)]+ (R′′ t H, Me, nC4H9) shows that chelating
coordination of the carbonyl group is favored over olefin coordination at room temperature. Formation of
chelates analogous to 2 during the copolymerization is assumed to render the subsequent monomer insertion
a turnover-limiting step.
Introduction
The development of polymerization catalysts incorporating
late transition metals is a promising area of research, since late
metals are typically less oxophilic, and thus more functional-
group tolerant, than early metals. For example, Ru-based
metathesis catalysts have been developed that are compatible
with a wide range of functional group-containing olefins and
are active in aqueous media.5 Examples of the functional-group
The development of an insertion-type olefin polymerization
catalyst compatible with readily available polar-functionalized
monomers H2CdCHX (X t e.g., C(O)OR, OC(O)R) would
potentially offer a low-pressure, low-temperature route to a wide
range of functionalized copolymers. This development might
enable the synthesis of new polymer structures or offer an
alternate route to commercially available copolymers such as
ethylene-acrylate and ethylene-vinyl acetate copolymers, which
are presently produced by radical polymerizations in high-
pressure reactors.1 Although Ziegler-Natta and related catalysts
based on early transition metal d0-complexes are extensively
used for the coordination polymerization of nonpolar olefins
such as ethylene and propylene, the use of these catalysts in
the copolymerization of functionalized olefins has been limited
due to their highly oxophilic nature.2 For example, the
polymerizations by early metals of olefins containing a func-
tional group in a remote position to the vinyl group have been
reported, but these reactions are currently limited to special
substrates.3,4
(2) As leading references, see: (a) Coates, G. W.; Waymouth, R. M.
Science 1995, 267, 217-219. (b) Yang, X.; Stern, C. L.; Marks, T. J. J.
Am. Chem. Soc. 1994, 116, 10015-10031. (c) Coughlin, E. B.; Bercaw, J.
E. J. Am. Chem. Soc. 1992, 114, 7606-7607. (d) Crowther, D. J.; Baenziger,
N. C.; Jordan, R. F. J. Am. Chem. Soc. 1991, 113, 1455-1457. (e)
Kaminsky, W.; Ku¨lper, K.; Brintzinger, H. H.; Wild, F. R. W. P. Angew.
Chem., Int. Ed. Engl. 1985, 24, 507-508. (f) Ewen, J. A. J. Am. Chem.
Soc. 1984, 106, 6355-6364. For recent reviews, see: (g) Brintzinger, H.
H.; Fischer, D. Mulhaupt, R.; Rieger, B.; Waymouth, R. Angew. Chem.,
Int. Ed. Engl. 1995, 34, 1143-1170. (h) Coates, G. W.; Waymouth, R. M.
In ComprehensiVe Organometallic Chemistry II; Abel, E. W., Stone, F. G.
A., Wilkinson, G., Eds.; Hegedus, L., Vol. Ed.; Pergamon Press: 1995;
Vol. 12, pp 1193-1208.
(3) (a) Chung, T. C. Macromolecules 1988, 21, 865-869. (b) Chung,
T. C.; Rhubright, D. Macromolecules 1993, 26, 3019-3025. (c) Kesti, M.
R.; Coates, G. W.; Waymouth, R. M. J. Am. Chem. Soc. 1992, 114, 9679-
9680. (d) Aaltonen, P.; Lo¨fgren, B. Macromolecules 1995, 28, 5353-5357.
(e) Galimberti, M.; Giannini, U.; Albizatti, E.; Caldari, S.; Abis, L. J. Mol.
Catal. 1995, 101, 1-10.
† University of North Carolina at Chapel Hill.
‡ DuPont Central Research and Development.
(1) Doak, K. W. In Encyclopedia of Polymer Science and Engineering;
Mark, H. F., Ed.; John Wiley and Sons: New York, 1986; Vol. 6, pp 386-
429.
(4) The preparation of ethylene-acrylate A-B block-copolymers has
recently been reported. However, the ethylene block must be grown first,
presumably due to an irreversible change in polymerization mechanism:
Yasuda, H.; Ihara, E. Macromol. Chem. Phys. 1995, 196, 2417-2441.
S0002-7863(96)04144-3 CCC: $15.00 © 1998 American Chemical Society
Published on Web 01/27/1998

Pd-Catalyzed Copolymerization of Ethylene and R-Olefins
J. Am. Chem. Soc., Vol. 120, No. 5, 1998 889
Scheme 1
R-olefins.14 The palladium complexes also catalyze the co-
polymerization of ethylene and R-olefins with functionalized
olefins such as acrylates and methyl vinyl ketone.15 A key
feature of these Ni and Pd catalysts is the incorporation of bulky
substituents R′ on the aryl groups of the R-diimine ligand, which
block associative olefin exchange and thus effectively retard
chain transfer (Scheme 2).14,16 We present here a full account
of the mechanistic aspects of the copolymerization of ethylene
and R-olefins with methyl acrylate. The effect of catalyst
structure and reaction conditions is discussed based on mecha-
nistic insight obtained from low-temperature NMR experiments.
Full details of the characterization of the unique, highly branched
copolymers17 and the functional-group tolerance of these
catalysts18,19 will be reported separately.
tolerance of late metals in insertion-type reactions include reports
on Ru, Rh, Ni, and Pd catalysts for the dimerization of acrylates
and the codimerization of ethylene and acrylates.6,7 In these
acrylate dimerizations and in numerous other insertion reactions
of late metals with olefins, â-hydride elimination competes
effectively with chain growth, resulting in the formation of
dimers or oligomers.6,8 A prominent example is the synthesis
of linear R-olefins from ethylene in the Ni-catalyzed Shell
Higher Olefin Process.8a,b Recently, however, a number of
ethylene polymerization catalysts based on Co, Rh, and Ni have
been described.9 Although the polymerization of R-olefins by
these catalysts has not been achieved,10,11 a Ni catalyst has been
reported to copolymerize ethylene with olefins containing a
functional group in a remote position to the olefin.12,13
Results and Discussion
A. Copolymerization Reactions. Employing cationic pal-
ladium catalysts with bulky substituted R-diimine ligands to
copolymerize ethylene or an R-olefin with methyl acrylate yields
a high molecular weight random copolymer (eq 1). Similar to
the corresponding ethylene or R-olefin homopolymers synthe-
sized with these catalysts, the copolymers are highly branched,
the ester groups being located predominantly at the ends of
branches in the manner shown (x g 0).17
We recently reported the development of highly active,
cationic Ni(II)- and Pd(II)-based catalysts of the general type
[(N∧N)M(Me)(L)]+ (Scheme 1) that polymerize ethylene and
(5) As leading references, see: (a) Moore, J. S. In ComprehensiVe
Organometallic Chemistry II; Abel, E. W., Stone, F. G. A., Wilkinson, G.,
Eds.; Hegedus, L., Vol. Ed.; Pergamon Press: 1995; Vol. 12, pp 1209-
1232, and references therein. (b) Novak, B. M.; Grubbs, R. H. J. Am. Chem.
Soc. 1988, 110, 7542-7543. (c) Nguyen, S. T.; Johnson, L. K.; Grubbs, R.
H. J. Am. Chem. Soc. 1992, 114, 3974-3975. (d) Lynn, D. M.; Kanaoka,
S.; Grubbs, R. H. J. Am. Chem. Soc. 1996, 118, 784-790. (e) Stumpf, A.
W.; Saive, E.; Demonceau, A.; Noels, F. J. Chem. Soc., Chem. Commun.
1995, 1127-1128.
(6) (a) Alderson, T.; Jenner, E. L.; Lindsey, R. V., Jr. J. Am. Chem.
Soc. 1965, 87, 5638-5645. (b) Barlow, M. G.; Bryant, M. J.; Haszeldine,
R. N.; Mackie, A. G. J. Organomet. Chem. 1970, 21, 215-226. (c) Oehme,
G.; Pracejus, H. Tetrahedron Lett. 1979, 343-344. (d) Nugent, W. A.;
Hobbs, F. W., Jr. J. Org. Chem. 1983, 48, 5364-5366. (e) Grenouillet, P.;
Neibecker, D.; Tkatchenko, I. Organometallics 1984, 3, 1130-1132. (f)
Nugent, W. A.; McKinney, R. J. J. Mol. Catal. 1985, 29, 65-76. (g)
McKinney, R. J.; Colton, M. C. Organometallics 1986, 5, 1080-1085. (h)
Wilke, G. Angew. Chem. 1988, 100, 189-211. (i) Brookhart, M.; Sabo-
Etienne, S. J. Am. Chem. Soc. 1991, 113, 2777-2779. (j) Brookhart, M.;
Hauptman, E. J. Am. Chem. Soc. 1992, 114, 4437-4439. (k) Hauptman,
E.; Sabo-Etienne, S.; White, P. S.; Brookhart, M.; Garner, J. M.; Fagan, P.
J.; Calabrese, J. C. J. Am. Chem. Soc. 1994, 116, 8038-8060, and references
cited therein. (l) DiRenzo, G. M.; White, P. S.; Brookhart, M. J. Am. Chem.
Soc. 1996, 118, 6225-6234.
The chelate complexes 2 or the nitrile adducts 3 and 4 were
generally preferred to the ether-adducts 1 for preparative-scale
(12) Klabunde, U.; Ittel, S. D. J. Mol. Catal. 1987, 41, 123-134.
(13) A palladium-catalyzed reaction of ethylene with methyl acrylate
has been reported to give low molecular weight materials (Mn e 4100),
but no detailed product characterizations were given: Drent, E.; Pello, D.
H. L.; Jager, W. W. Eur. Pat. Appl. 1994, 589527.
(14) Johnson, L. K.; Killian, C. M.; Brookhart, M. J. Am. Chem. Soc.
1995, 117, 6414-6415 (experimental details and NMR data are given in
the Supporting Information).
(15) Johnson, L. K.; Mecking, S.; Brookhart, M. J. Am. Chem. Soc. 1996,
118, 267-268 (experimental details and NMR data are given in the
Supporting Information).
(16) The use of R-diimine ligands in transition-metal-catalyzed reactions
has been extensively researched. As leading references, see: (a) van Koten,
G.; Vrieze, K. AdV. Organomet. Chem. 1982, 21, 151-239. (b) van Asselt,
R.; Gielens, E. E. C. G.; Rulke, R. E.; Vrieze, K.; Elsevier: C. J. J. Am.
Chem. Soc. 1994, 116, 977-985. For the development and synthesis of the
N-aryl-substituted R-diimine ligands used in this research, see: (c) R ) H,
Me: tom Dieck, H.; Svoboda, M.; Grieser, T. Z. Naturforsch 1981, 36b,
823-832. (d) R ) An: van Asselt, R.; Elsevier: C. J.; Smeets, W. J. J.;
Spek, A. L.; Benedix, R. Recl. TraV. Chim. Pays-Bas 1994, 113, 88-98.
(17) The detailed nature of the branching in the novel ethylene- and
R-olefin polymers and the corresponding copolymers with functionalized
olefins has been extensively studied by 2D-13C NMR spectroscopy: McLain,
S.; McCord, E., manuscript in preparation.
(18) For example, methyl vinyl ketone, numerous acrylates besides MA
(e.g., acrylic acid), and other polar monomers have been copolymerized
with ethylene by the palladium catalysts.15,19 In addition, polymerizations
using the palladium catalysts have been carried out in water.19 The synthesis
and reactivity of nickel chelate complexes and the functional-group tolerance
of the nickel catalysts has also been explored.19
(7) Behr, A. In Industrial Applications of Homogeneous Catalysis;
Mortreux, A., Petit, F., Eds.; D. Reidel Publishing Company: Dordrecht,
1988; pp 156-167.
(8) (a) Peuckert, M.; Keim, W. Organometallics 1983, 2, 594-597. (b)
Keim, W. Angew. Chem., Int. Ed. Engl. 1990, 29, 235-244. (c) Rix, F. C.;
Brookhart, M. J. Am. Chem. Soc. 1995, 117, 1137-1138.
(9) (a) Keim, W.; Kowaldt, F. H.; Goddard, R.; Kru¨ger, C. Angew. Chem.,
Int. Ed. Engl. 1978, 17, 466-467. (b) Schmidt, G. F.; Brookhart, M. J.
Am. Chem. Soc. 1985, 107, 1443-1444. (c) Brookhart, M.; Volpe, Jr., A.
F.; Lincoln, D. M.; Horvath, I. T.; Millar, J. M. J. Am. Chem. Soc. 1990,
112, 5634-5636. (d) Ostaja Starzewski, K. A.; Witte, J.; Reichert, K. H.;
Vasiliou, G. In Transition Metals and Organometallics as Catalysts for
Olefin Polymerization; Kaminsky, W., Sinn, H., Eds.; Springer-Verlag:
Berlin Heidelberg, 1988; pp 349-360. (e) Wang, L.; Lu, R. S.; Bau, R.;
Flood, T. C. J. Am. Chem. Soc. 1993, 115, 6999-7000.
(10) Certain Ni(II) catalysts convert R-olefins to oligomers with degrees
of polymerization of ca. 4-20: (a) Mo¨hring, V. M.; Fink, G. Angew. Chem.,
Int. Ed. Engl. 1985, 24, 1001-1003. (b) Schubbe, R.; Angermund, K.; Fink,
G.; Goddard, R. Macromol. Chem. Phys. 1995, 196, 467-468.
(11) For an early example of the observation of both 2,1- and 1,2-
insertions in R-olefin dimerizations by Pd(II)-based catalysts modified with
bipyridyl-type ligands, see: (a) Drent, E. Eur. Pat. Spec. 1986, 170311.
(b) Drent, E. Pure Appl. Chem. 1990, 62, 661-669.
(19) (a) Brookhart, M. S.; Johnson, L. K.; Killian, C. M.; Arthur, S. D.;
Feldman, J.; McCord, E. F.; McLain, S. J.; Kreutzer, K. A.; Bennett, A.
M.; Coughlin, B. E.; Ittel, S. D.; Parthasarathy, A.; Tempel, D. J. Pat. Appl.
WO 96/23010, 1996. (b) Brookhart, M. S.; Arthur, S. D.; Feldman, J.;
Johnson, L. K.; McLain, S. J.; McCord, E. F.; Mecking, S.; Wang, L.; Wang,
Y., unpublished results.

890 J. Am. Chem. Soc., Vol. 120, No. 5, 1998
Mecking et al.
Scheme 2
Table 1. Ethylene-MA Copolymerization and Ethylene Homopolymerization: Effect of Reaction Conditionsf
results
polymer properties
react. conditions
[MA] (M)
p(atm)e
TONd
a
polymer
yield (g)
comon.
Mn
branches/
1000C
entry
cat.
incorp.b (%)
E
MA
(× 10-3
)
Mw/Mn
1
2
3
4
5
6
7
8
2b
2b
2b
2b
2b
2b
2b
2d
0.6
2.9
5.8
5.8
2
2
2
6
2
22.2
4.3
1.8
11.2
8.8
13.7
8.1
1.0
6.1
12.1
4.0
7710
1290
455
78
84
63
88
26
11
42
1.8
1.6
1.6
1.8
3.5c
2.7c
3.0c
103
103
105
97
102
100
98
3560
148
30160
48700
28480
13300
297c
490c
11
29
11
496c
3.7
445/28c
106
aDetermined by GPC vs polystyrene standards, uncorrected. b Mol %. c Bimodal distribution. d Turnover number t mole substrate converted per
mole catalyst. e E.g. 2 atm t 1 atmg. f 0.1 mmol catalyst (entries 5-8: 0.01 mmol); solvent: CH2Cl2 (total volume CH2Cl2 and comonomer: 100
mL); temperature: 35 °C (entries 5-8: 25 °C); reaction time: 18.5 h.
polymerizations, as the former are air- and temperature-stable
studied extensively using ethylene and methyl acrylate (MA)
as comonomers. The effect of monomer concentrations is
shown in Table 1. Gas solubility experiments showed that the
solubility of ethylene in neat MA and in methylene chloride
(used as a solvent in copolymerization experiments) does not
differ significantly. Thus, varying the MA concentration at a
given ethylene pressure does not change the ethylene concentra-
tion. The solubility of ethylene in methylene chloride was
determined to be 0.18 mol/L atm in the range from 1 to 11 atm
at 25 °C. The fraction of MA incorporation is directly
proportional to the MA concentration in the reaction solution
(Table 1, entries 1-3 and Figure 1). The polymer yield falls
as the MA incorporation increases, due to a decrease in ethylene
turnovers, while the turnover numbers for MA remain roughly
the same. In comparison to ethylene homopolymerization
experiments22 (Table 1, entries 5-8), productivities of the
copolymerizations are greatly reduced. These observations are
in accord with the mechanistic model depicted in Scheme 3,
which is supported by low-temperature NMR experiments (vide
infra). After an insertion of acrylate, rearrangement can yield
a stable chelate complex. Coordination of the carbonyl group
to palladium inhibits the next olefin insertion and renders it a
turnover-limiting step.
and can be prepared readily from [(N∧N)PdMeCl], NaBAr′4 and
the acrylate or nitrile.20 Under the conditions reported here,
the results of polymerization experiments were largely inde-
pendent of the precursor employed.21
1. Copolymerization of Ethylene with Methyl Acrylate.
The effects of catalyst structure and reaction parameters were
(20) The high lability of Et2O results in the thermal instability of 1;
however, the lability of Et2O also makes 1 a very useful precursor for low-
temperature NMR studies. Decomposition of 1 (R′ ) i-Pr) occurs upon
activation of one of the CH3 bonds of the isopropyl substituent by Pd,
resulting in the evolution of methane and formation of a chelate complex:
Johnson, L. K.; Tempel, D.; Brookhart, M., unpublished results.
(21) Concerning activation of ethylene homopolymerizations using
chelates 2 as catalyst precursors, the relative amount of unactivated chelate
2b was determined by 1H NMR analysis (integrals of OMe-groups) of the
ester end group of the polymer vs the unreacted chelate in 1 h runs. After
1 h, at 2 atm 71% of the chelate had been activated, whereas at 29 atm
virtually no unactivated chelate remained. These data correspond well to
the productivities observed in these experiments and to productivity observed
using the ether complex 1, which is activated instantaneously, as a catalyst
precursor. Thus, the rate of activation of 2 is only significant at low ethylene
pressure in combination with short reaction times; in 18 h experiments,
even at only 1 atm, the rate of activation does not affect the outcome of
polymerizations significantly.
(22) Additional data for Pd-catalyzed homopolymerizations of ethylene
(1 atm) and R-olefins by the Et2O adducts 1 is published in Table 1 of ref
14. Please note, in this table Mn and Mw reported in entry 1 for the ethylene
homopolymer produced by 1a are off by a factor of 10; correct values are
Mn ) 6 000 and Mw ) 18 000. The low values for the molecular weights
of the Pd-produced homopolymers in ref 14 as compared to the values
reported in Table 1 of this report are mainly due to mass-transfer-limited
conditions in ref 14.

Pd-Catalyzed Copolymerization of Ethylene and R-Olefins
J. Am. Chem. Soc., Vol. 120, No. 5, 1998 891
Scheme 3
time in the range of 24-72 h had little effect on polymer
molecular weight. A run under identical conditions as entry 2
in Table 2 (18 h) terminated after 3 h yielded a polymer of
2-fold lower molecular weight (Mn ) 23 kg/mol; 870 TO). That
is, in the 3 h experiment the rate of chain transfer is on the
order of the reaction time, whereas in the longer experiments,
the molecular weight is controlled by chain transfer and thus
reflects the properties of the specific catalyst under steady state
conditions of chain initiation and chain transfer. Assuming that
the copolymerization is retarded by formation of a chelate as a
stable catalyst resting state as discussed above, but with
otherwise identical mechanisms of chain propagation and chain
transfer operating as in the case of ethylene homopolymerization,
one would expect the molecular weights of the copolymers to
approach those of the homopolymers at sufficiently long reaction
times. However, the molecular weights of the copolymers are
much lower than those of ethylene homopolymers. Additional
modes of chain transfer must be operative. Possibly, intermedi-
ates of the type [(N∧N)PdH{RCHdCHC(O)OMe}]+ are in-
volved. It is interesting in this respect that for 2c, a slow
reaction with excess MA resulted in elimination of the chelate
moiety and formation of a new chelate [(N∧N)Pd{(CH2)2C(O)-
OMe}]+. In addition, exposure of 2a to 6000 equiv of MA for
18 h (0.02 mmol; 10 mL MA; 10 mL methylene chloride)
resulted in decomposition of the complex and formation of a
small amount of MA-dimers, predominantly dimethyl hex-3-
enedioate. In the absence of excess MA, 2a is stable in
methylene chloride solution for days.
Figure 1. Linear dependence of MA incorporation on the MA
concentration in the reaction solution.
Correspondingly, increasing the ethylene pressure results in
an increase in ethylene and MA turnovers (Table 1, entry 4 vs
3). The monomer concentrations have no significant effect on
the total number of methyl- and ester-ended branches for a given
catalyst. The number of branches observed is similar to that
for the corresponding ethylene homopolymers (entries 5-7).
This suggests that chain-running (Scheme 2) is fast compared
to chain growth in the case of the palladium catalysts. In all
experiments given in Tables 1 and 2, the ester groups are
predominantly located at the ends of branches with x g 2 (see
eq 1). The average length of the ester-ended branch decreases
with increasing ethylene pressure; that is, after an MA-insertion
the resulting Pd-alkyl complex may be trapped prior to
isomerization to a six-membered chelate or further chain
running.17,23
The mechanistic experiments depicted in eq 2 (vide infra)
revealed that MA binds to the electrophilic metal center via its
olefinic functionality (as opposed to coordination via its ester
group).26 To further probe for solvent effects or other effects
of the ester functionality of the MA monomer present in the
copolymerization reactions, an ethylene homopolymerization
was run in a 3:1 mixture (v:v) of methylene chloride and methyl
propionate under conditions otherwise identical with entry 6 of
Table 1. Productivity and polymer molecular weight are
reduced (32 000 TO; Mn ) 306 kg/mol), but compared to the
copolymerization experiments the effect is small, and it can be
concluded that the presence of ester groups in the reaction
mixture does not significantly effect the outcome of polymer-
ization experiments with these catalysts.
Figures 2 and 3 show the progress of the copolymerization
over time. Catalyst deactivation occurs within 50 h with the
ArNdC(Me)-C(Me)dNAr (Ar t 2,6-C6H3(i-Pr)2) ligand (b)
(Figure 2), whereas for the catalyst with the corresponding 2,6-
dimethyl substituted ligand d (Figure 3), no loss in activity was
observed for over 3 days.24,25 In both cases, varying the reaction
(24) The instability of complexes containing the 2,6-diisopropyl-
substituted ligand as compared to the 2,6-dimethyl-substituted ligand may
be related to the greater accessibility of the C-H bond of the i-Pr substituent
to the metal center.20
(25) In homopolymerizations using 2d, turnover frequency in a 1 h
experiment was the same as that in the 18.5 h experiment (entry 8, Table
1) under identical conditions. This implies little or not catalyst deactivation
over 18 h.
(23) The observation that chain running is fast relative to chain growth
in general, whereas the intermediate formed after an MA-insertion may be
trapped by ethylene, is in accord with the result that rearrangement of the
chelate complexes (eq 1) is much slower than isomerization of an
unsaturated or weakly ligated alkyl complex [(N∧N)PdR(L)]+ (L t solvent;
agostic interaction): Tempel, D. J.; Johnson, L. K.; Brookhart, M.,
unpublished results.

892 J. Am. Chem. Soc., Vol. 120, No. 5, 1998
Mecking et al.
Table 2. Ethylene-MA Copolymerization: Effect of the R-Diimine Liganda
ligand
results
polymer properties
TONd
MA-incorp.b
(%)
Mn
branches/
1000C
a
subst. of aryl
ring Ar-Nd
rctn.
cond.
polymer
yield (g)
entry
-NdC(R)-
E
MA
(×10-3
)
Mw/Mn
1
2
3
4
5
6
7
8
9
a
b
c
d
b
H
2,6-iPr2
A
A
A
A
B
B
B
B
B
1.2
11.2
1.2
2.3
8.5
4.0
2.5
3.0
3.6
5.0
4.0
4.7
14.2
7
15
20
355
3560
364
542
827
283
154
162
266
19
148
18
90
58
50
41
54
47
0.3c
42
10
7
n.d.
97
Me
An
Me
Me
Me
Me
Me
Me
2,6-iPr2
1.8
1.8
2.1
1.4
1.3
1.4
1.4
1.4
2,6-iPr2
109
116
128
170
203
255
178
2,6-Me2
2,6-iPr2
17
12
8
8
7
2-iPr 6-Me
2,6-Me2
2,4,6-Me3
2,6-Me2 4-Br
d
25
15
a Determined by GPC vs polystyrene standards, uncorrected. b Mol %. c Determined by 1H NMR spectroscopy of the nonvolatile product fraction;
ca. 0.5 g of volatile products were formed additionally. d Turnover number t mole substrate converted per mole catalyst. e Reaction conditions A:
0.1 mmol catalyst precursor 2; solvent: 50 mL of CH2Cl2; 50 mL of MA (t 6 M); 6 atm (i.e., 5 atmg); temperature: 35 °C; reaction time: 18.5
h. B: 0.3 mmol catalyst precursor 3; solvent: 40 mL CH2Cl2; 5 mL MA (t 1.2 M); 1 atm (ambient pressure); temperature: 25 °C; reaction time:
72 h.
Figure 2. Reaction profile of ethylene-MA copolymerization employing ligand ArNdC(Me)-C(Me)dNAr (Ar t 2,6-C6H3(i-Pr)2) (b). Reaction
conditions of entry 5, Table 2.
Table 2 shows the effects of variations of ligand structure
on the copolymerizations. Variation of the diimine backbone
substituents R does not significantly affect the percentage of
acrylate incorporation in the copolymer (Table 2, entries 1-3).
However, the nature of R affects productivities (Me > An ≈
H) and molecular weights (Me > An > H), and the trends
follow those observed for the ethylene homopolymerizations.14
Reduction of the steric bulk of the substituents on the aryl
moieties R′ results in an increase of the relative acrylate
incorporation, presumably due to the greater accessibility of the
metal center for the binding of the sterically larger olefin (Table
2, entry 2 vs 4 and 5-7). However, at the same time, less
effective retardation of associative olefin exchange enhances
chain transfer and thus lowers the molar mass of the copolymer.
(26) (a) To convert 1a completely to 5a in a reasonable time at
temperatures low enough to prevent migratory insertion, an excess of MA
was utilized. This results in formation of an additional species, identi-
fied as the MA adduct of 6a, [(N∧N)Pd{CH(Et)C(O)OMe}-
{H2CdCHC(O)OMe}]+ (t at δ 0.53, J ) 7 Hz (CD2Cl2, -62 °C)). This
does not effect the rate of migratory insertion, which was found to be
independent of [MA] in the range of 1.3-18 equiv MA in the limit of
error. Some subsequent rearrangement of 6a to 7a also occurred. (b) Starting
from 1b, displacement of ether by MA occurs more slowly than with 1a
and thus interferes with observation of the migratory insertion. Therefore,
complexes of ligand a were preferred for mechanistic studies. In addition
to the η2-olefin complex 5b (1H NMR (CD2Cl2, -71 °C) δ 5.01 (d, 1, J )
15 Hz, dCHH′), 4.82 (dd, 1, J ) 15 Hz, J ) 8 Hz, dCHC(O)), 4.48 (d,
1, J ) 8 Hz, dCHH′), 3.60 (s, 3; OMe), 2.38 and 2.27 (s, 3 each; NdC-
(Me)-C′(Me)dN), 0.32 (s, 3; PdMe)), a second species 5b′ with δ 2.96 (s,
3, OMe), 2.18 (s, 6, NdC(Me)-C′(Me)dN), 0.26 (s, 3H.; PdMe) (CD2Cl2,
-71 °C) is observed. The latter is assigned as the κ-O complex analogous
to 5b, in which the MA-ligand is bound via its carbonyl group. At -71 °C,
conversion of 5b′ to 5b was observed (in addition to migratory insertion).
This rearrangement presumably occurs very rapidly at room temperature,
so that coordination of the acrylate via the carbonyl-group is relatively
insignificant in typical copolymerization experiments.
Interpretation of the relative catalyst activities is complex:
mechanistic experiments (vide infra) suggest that opening of a
chelate complex by ethylene coordination, believed in part to
control the TO frequency of the copolymerization reaction, is
favored by smaller diimine substituents R′. On the other hand,
the smaller diimine substituents also result in lower catalyst
activity in ethylene homopolymerization experiments due to
slower chain growth (entry 6 vs 8 in Table 1). For example,
for the production of a copolymer of given MA incorporation

Pd-Catalyzed Copolymerization of Ethylene and R-Olefins
J. Am. Chem. Soc., Vol. 120, No. 5, 1998 893
Figure 3. Reaction profile of ethylene-MA copolymerization employing ligand ArNdC(Me)-C(Me)dNAr (Ar t 2,6-C6H3Me2) (d). Reaction
conditions of entry 7, Table 2.
Table 3. R-Olefin-MA Copolymerizationsc
rctn. cond.
results
polymer properties
TON
polymer MA-incorp.b
Mn
branches/
1000C
a
reaction
conc.
conc.
entry
R-olefin
catalyst time (h) R-olefin MA (m) yield (g)
(%)
R-olefin MA (×10-3
)
Mw/Mn
1
2
3
4
5
propene
hexene
hexene
dodecene
hexene
2b
4b
4b
4b
2d
18.5
18.5
39
18.5
18.5
6 atm
1.6 M
1.6 M
1.6 M
1.7 M
0.6
1.2
1.2
1.2
1.1
5.0
1.1
10.3
11.4
11.8
20.3
1179
187
313
157
343
13
22
40
21
87
37
24
30
46
1.8
1.6
1.9
1.4
1.5
213
91
94
52
88
0.92
1.53
1.39
1.43
26
a Determined by GPC vs polystyrene standards, uncorrected. b Mol %. c Reaction conditions: 0.05 mmol catalyst precursor (entry 1: 0.1 mmol,
entry 5: 0.039 mmol); solvent: CH2Cl2 (total volume solvent and monomers: 50 mL, entry 1: 100 mL); temperature: 25 °C (entry 1: 35 °C).
by catalyst 2b (R′ ) i-Pr) and catalyst 2d (R′ ) Me), a similar
rate was observed with both catalysts (entry 3 of Table 1 vs
entry 4 of Table 2). Electron-releasing or -withdrawing
substituents were introduced in the p-position of the aryl ring
(entries 7-9 of Table 2). With more electron-rich ligands, a
higher acrylate incorporation is observed.27 Presumably, binding
of the electron-deficient olefin relative to ethylene is increased
by decreasing the electrophilicity of the metal center. Again,
interpretation of the relative activities is not straightforward.
2. Copolymerization of r-Olefins with Acrylates. The
cationic palladium diimine catalysts are also effective for the
copolymerization of R-olefins with functionalized olefins (Table
3). The NMR spectra of the copolymers show that they possess
structures similar to the ethylene copolymers with respect to
the predominant location of ester groups at the ends of
branches.17 As is the case for the R-olefin homopolymers,14,17
the total branching is lower than would be expected for an
exclusive incorporation of the R-olefin in a 1,2-fashion. This
implies that a significant amount of 2,1-insertion occurs,
followed by “chain straightening” by migration of the metal
center to the terminal carbon atom. With long chain R-olefins
such as dodecene (entry 4), this enables the production of
copolymers with lower branching and different properties than
are accessible by ethylene copolymerization. For example, the
dodecene-MA copolymer from entry 4 has 52 branches per 1000
carbon atoms versus typically 100 branches for an ethylene-
MA copolymer.
Comparing the catalyst activity of R-olefin versus ethylene
copolymerizations for a polymer of a given molar acrylate
incorporation, the R-olefin copolymerizations are less productive
(entry 3, Table 1 vs entry 2, Table 3). In terms of the assumed
mechanism, formation of chelate complexes is expected to have
an even greater retarding effect in copolymerizations with
R-olefins than with ethylene, as mechanistic experiments show
that displacement of the chelating carbonyl group is less
effective with R-olefins (vide infra). Also, the lower rate of
migratory insertion of R-olefins in comparison to ethylene will
result in a lower polymerization rate.28
While under the same reaction conditions the R-olefin
copolymerization rates are lower than the ethylene copolymer-
ization rates, the relative percent acrylate incorporation is higher.
For example, the hexene-MA copolymerizations give a relative
incorporation of 7:1 of hexene to MA at equal molar concentra-
tions of the monomers, whereas for ethylene-MA it is ca. 150:
1. The higher incorporation of MA in the R-olefin copolymers
is the result of two factors: (a) the rates of olefin insertion into
(27) This appears to be a general trend, as a decrease in MA incorporation
upon placing electron-withdrawing chloro substituents in the meta and ortho
positions and an increase in MA incorporation upon placing donating
o-methoxy substituents on other series of N-aryl-substituted R-diimine
ligands have been observed: Wang, Y.; Wang, L.; Johnson, L. K.,
unpublished results.
(28) Migratory insertion of propene into a Pd-alkyl bond was found to
be ca. 3-fold slower than insertion of ethylene in complexes [(N∧N)PdR-
(olefin)]+.14

894 J. Am. Chem. Soc., Vol. 120, No. 5, 1998
Mecking et al.
a growing polymer chain are lower for R-olefins than for
ethylene,28 and (b) the difference in relative binding is smaller
between R-olefins and MA than between ethylene and MA,
although in both cases the acrylate binding is weaker (vide infra).
The effects of variations in ligand structure were examined
in the R-olefin copolymerizations. As in ethylene-MA copoly-
merizations, under identical reaction conditions a much higher
acrylate incorporation is observed in hexene-MA copolymeri-
zation with the less bulky substituted ligand d (R′ t Me) than
with its isopropyl-substituted analogue b (entry 2 vs 5, Table
3). At the same time, the polymer yield with d is lower than
with b in the ethylene-MA copolymerization, due to pronounced
rate-inhibiting chelate formation with the increased percentage
of acrylate insertions with d (entry 2 vs 4, Table 2). For
synthesis of an ethylene-MA copolymer of given acrylate
incorporation, similar productivities are observed with both
ligands; the lower rate of olefin migratory insertion with d is
apparently compensated by more facile chelate opening (entry
4, Table 2 vs entry 3, Table 1). In contrast, in hexene-MA
copolymerizations similar productivities are observed with b
and d under identical reaction conditions, despite the much
higher MA incorporation with d. Mechanistic experiments (vide
infra) suggest that in addition to chelate opening by olefins
generally being more facile with d in comparison to b, chelate-
opening by an R-olefin in comparison to opening by ethylene
is more favorable with d.
Figure 4. Eyring plot for migratory insertion of MA in 5a.
1, 1 h reaction time, 6 atm Versus ∆Gq(25 °C) ) 17.5 kcal/mol
as extrapolated from the low-temperature experiments). Given
these results, it is reasonable to use the insertion of MA into a
Pd-Me bond as a model for migratory insertion of MA into
the growing polymer chain.
B. Mechanistic Studies. Low-temperature NMR experi-
ments (eq 2) showed that the π-olefin complex 5a, formed upon
reacting the ether-adduct 1a with MA, undergoes migratory
insertion in a 2,1-mode with ca. 95% regioselectivity to yield
6a. Subsequent isomerization via 7a yields the six-membered
chelate 2a as the final, stable product. Only minor amounts of
the 1,2-insertion product 7′a are formed.29,30
2. Relative Binding Constants. The equilibrium constants
for the reaction depicted in eq 3 were determined for a variety
of ligands L and L′. Results are summarized in Table 4.31 The
relative trend in binding strength observed is ethylene >
R-olefins . acrylates.26b
In the copolymerization reaction, the relative incorporations
of the comonomers are determined by their relative insertion
rates and by their relative binding affinities to the metal center.
These factors were investigated by low-temperature NMR
spectroscopy using the methyl complexes [(N∧N)PdMe(olefin)]+
as model compounds.
The electron-deficient olefin MA binds so much more weakly
to the electrophilic metal center than ethylene that this equi-
librium constant could not be determined in a single pairwise
competition experiment. 4-Methoxystyrene was found to be a
suitable ligand of intermediate coordination strength. The
relative binding constant of ethylene vs propylene is similar to
that reported by Kurosawa et al. for [(C5H5)Pd(PPh3)(olefin)]-
1. Olefin Insertion Rates. The rate of migratory insertion
of MA into the Pd-Me bond of 5a to form 6a was followed
1
by H NMR spectroscopy at -75 to -62 °C. An Eyring plot
of rate data obtained (Figure 4) gave ∆Hq ) 12.1 ( 1.4 kcal/
mol, ∆Sq ) -14.1 ( 7.0 eu.26 We previously reported data
for olefin migratory insertion in the corresponding ethylene
complexes.14 In this case, the rates of subsequent ethylene
insertions into the growing polymer chain could also be
monitored by NMR spectroscopy and did not differ significantly
from the rate of the first insertion of ethylene into the Pd-Me
bond. Extrapolation of these data to room temperature is in
good agreement with the highest activities observed in ethylene
homopolymerization experiments (for 2b as catalyst precursor:
k ) 1.2 s-1 at 25 °C, ∆Gq ) 17.4 kcal/mol for conditions of
entry 6 Table
(29) The 2,1-insertion mode is normally observed for polar olefins. See,
for example: (a) Ozawa, F.; Hayashi, T.; Koide, H.; Yamamoto, A. J. Chem.
Soc., Chem. Commun. 1991, 1469-1470. (b) Hauptman, E.; Brookhart,
M.; Fagan, P. J.; Calabrese, J. C. Organometallics 1994, 13, 774-780.
(30) The percentage of the 2,1-insertion product formed decreases with
increased size of the backbone substituent (R) and particularly with increased
bulk of the acrylate substituent. For example, for the insertion of tert-
butylacrylate (R ) Me, R′) i-Pr), the regioselectivity of the insertion was
reversed with 63% of the product consisting of the 1,2-insertion product.15
(31) For relative binding constants of other ligands in similar phenan-
throline complexes, cf.: Rix, F. C.; Brookhart, M.; White, P. S. J. Am.
Chem. Soc. 1996, 118, 4746-4764.

Pd-Catalyzed Copolymerization of Ethylene and R-Olefins
J. Am. Chem. Soc., Vol. 120, No. 5, 1998 895
Table 4. Equilibrium Constants for [(N∧N)PdMe(L)]+ + L′ a [(N∧N)PdMe(L′)]+ + L (N∧N t ArNdC(H)-C(H)dNAr, Ar t 2,6--iPr2C6H3
(a))b
L
L′
T (°C)
Keq
∆G (kcal/mol)
ethylene
4-methoxystyrene
ethylene
ethylene
ethylene
4-methoxystyrene
MA
MA
propene
hexene
-95
-95
-95
-85
-85
(5.8 ( 1.2) × 10-3
(1.8 ( 0.4) × 10-4
(1.0 ( 0.3) × 10-6 a
(9.3 ( 1.9) × 10-2
(4.3 ( 0.9) × 10-1
1.8 ( 0.1
3.1 ( 0.1
4.9 ( 0.2a
0.9 ( 0.1
0.3 ( 0.1
a Calculated from Keq(ethylene vs 4-methoxystyrene) and Keq(4-methoxystyrene vs MA). b Determined by H NMR. Solvent: CD2Cl2.
1
Scheme 4
Table 5. Thermodynamic Data for Equilibria 2 + C2H4 a10 (R′′
t H)b
3. Chelate Opening. As models for the presumed catalyst
resting state, the reversible substitution of the chelating carbonyl
group in 2a-c by ethylene was investigated by low-temperature
NMR spectroscopy (eq 4). Study of the temperature dependence
of the equilibria 2 + C2H4 h 10 (R′′ t H) provided the
thermodynamic data given in Table 5.
complex
∆H° (kcal/mol)
∆S° (eu)
Keq(35 °C)a
2a
2b
2c
2d
-8.1 ( 0.2
-5.3 ( 0.3
-5.7 ( 0.1
-6.7 ( 0.3
-34 ( 1
-31 ( 2
-27 ( 1
-29 ( 1
2 × 10-2
1 × 10-3
1 × 10-2
3 × 10-2
a Extrapolated. b Determined by 1H NMR at -100 to -58 °C.
Solvent: CD2Cl2.
ClO4.32 Surprisingly, 1-hexene binds more strongly than
propylene, and it must be assumed that the higher steric demand
is overridden by electronic factors. Considering the use of nitrile
complexes as catalyst precursors, it was found that nitriles are
of similar coordination strength as olefins. For 3b + C2H4 h
8b + CH3CN (eq 3, L′ t ethylene, L t CH3CN, CD2Cl2
solvent), Keq(-85 °C) ) (4.6 ( 0.9) × 10-2, ∆G° ) 1.2 ( 0.1
kcal/mol was determined. Comparing 3,5-bis(trifluoromethyl)-
benzonitrile with acetonitrile, the aromatic nitrile was found to
bind 10-fold less strongly at room temperature (CD2Cl2). Due
to the large excess of monomers present in polymerization
reactions, the equivalent of nitrile introduced with the catalyst
precursor should have at most a slightly inhibiting effect in the
copolymerization experiments.
Extrapolation shows that at room-temperature chelating
coordination of the carbonyl group is favored over ethylene
binding in all cases for the methyl acrylate chelate complexes.34
For example, the equilibrium constant Keq for 2b + C2H4 h
10b (R′′ t H) given in Table 5 corresponds to a ratio of 2b/
10b of 1000:1 under typical reaction conditions of the co-
polymerization experiments (6 atm ethylene). Replacement of
R′ t iPr by less bulky methyl groups (2d vs 2b) results in more
facile ethylene coordination. Thus under 6 atm of ethylene,
the ratio of 2d/10d is 30:1 at 35 °C.
Chelate opening with R-olefins is even less favorable than
with ethylene. The large excess of olefin required affects the
Extrapolating the above data to the conditions of the
copolymerization reaction (35 °C), the overall picture shown
in Scheme 4 is obtained.33 Applying the equation depicted in
Scheme 4 to the conditions of entry 1 in Table 2 (i.e., [MA] )
6 mol/L, [ethylene] ) 1 mol/L), an acrylate incorporation of 4
mol % is calculated, which matches reasonably well with the
5.0 mol % observed. This agreement supports the applicability
of the low-temperature NMR studies in modeling the copoly-
merization reaction. Thus, further studies may provide a
detailed understanding of how the structure of the diimine ligand
influences the properties and performance of the catalyst.
1
quality of the H NMR spectra; thus no thermodynamic data
was obtained, and only approximate values of equilibrium
constants are reported. For propylene, Keq(-99 °C) ≈ 1 L/mol
was determined for 2a + C3H6 h 10a (R′′ t Me), and for
1-hexene Keq(-99 °C) ≈ 2 L/mol (R′′ t C4H9). Compared to
the equilibrium constant of ethylene at the same temperature,
Keq(R-olefin)/Keq(ethylene) is ca. 0.003. As in the case of
(34) Chelate opening can be facilitated by the placement of electron-
withdrawing substituents on the chelate complex. For example, the insertion
of fluorinated octyl acrylate [FOA, (H2CdCHC(O)OCH2(CF2)6CF3] yields
an isolable chelate complex. The ring-opened form of the FOA chelate
complex l0a can be observed at -30 °C, a temperature at which ethylene
insertion readily occurs. Consequently, productivities in ethylene/FOA
copolymerizations are comparable to ethylene homopolymerization reac-
tions: (a) Reference 15. (b) Brookhart, M. S.; Johnson, L. K., Wang, L.,
unpublished results.
(32) Kurosawa, H.; Majima, T.; Asada, N. J. Am. Chem. Soc. 1980, 102,
6996-7003.
(33) The rate of ethylene insertion was obtained from a 1 h homo-
polymerization experiment (conditions of Table 1 entries 5-8, 2a, 29 atm).

896 J. Am. Chem. Soc., Vol. 120, No. 5, 1998
Mecking et al.
were calculated according to the derivation of Girolami et al.35 Errors
in ∆H° and ∆S° were calculated from the standard deviations of the
slope and intercept of van’t Hoff plots. A 20% error is assumed for
the equilibrium constants given in Table 4. Elemental analyses were
performed by Oneida Research Services of Whitesboro, NY, and by
Galbraith Laboratories, Inc., TN. IR spectra were obtained on a Mattson
Instruments 10410 FT spectrometer. GC analyses were run on a
Hewlett-Packard 5890 gas chromatograph equipped with a 30 m J&W
Scientific DB-5 column. Gel permeation chromatography was per-
formed on a Waters 150 CV chromatograph with Ultrastyragel columns
of 100-, 500-, 103-, 104-, and 105-Å porosities in THF vs polystyrene
standards. For thermal analysis a Seiko Instruments DSC220C
differential scanning calorimeter was used.
Materials. Hexane, pentane, and diethyl ether were distilled under
nitrogen from sodium benzophenone ketyl. Methylene chloride was
distilled under nitrogen from P2O5. Methylene chloride-d2 was dried
over CaH2, vacuum-transferred, degassed by repeated freeze-pump-
thaw cycles, and stored over 4 Å molecular sieves. Chloroform-d was
dried over 4 Å molecular sieves. Polymer grade ethylene and propylene
were used as received for both the bulk polymerizations and NMR
experiments. Methyl acrylate (stabilized with 200 ppm 4-methoxy-
phenol), 1-hexene, and 1-dodecene were dried over 4 Å sieves prior to
use. Na(BAr′4)36 (Caution! Trifluoromethyl-substituted aryl Grig-
nards can explode!37 ) and the complexes [(ArNdC(R)-C(R)dNAr)-
Pd(Me)(OEt2)](BAr′4)14 (R t H (1a) or Me (1b); Ar t 2,6-iPr2C6H3)
was prepared according to the published procedure. R-Diimine ligands
(ArNdC(R)-C(R)dNAr) were prepared according to literature
methods,16c,d and [(ArNdC(Me)-C(Me)dNAr)Pd(Me)(Cl)] (Ar t 2,6-
Me2C6H3) was prepared in an analogous manner to the procedure
published for the corresponding compound with Ar t 2,6-iPr2C6H3.14
Spectral Data for the (BAr′4)- Counterion. The 1H NMR
resonances of the [B{3,5-C6H3(CF3)2}4]- anion in CD2Cl2 were invariant
for different complexes and temperatures and are not repeated in the
spectroscopic data for each of the cationic complexes: 1H NMR
(CD2Cl2) δ 7.74 (s, 8, Ho), 7.57 (s, 4, Hp); 13C NMR (CD2Cl2) δ 162.2
(q, JCB ) 37.4, Cipso), 135.2 (Co), 129.3 (q, JCF ) 31.3, Cm), 125.0 (q,
JCF ) 272.5, CF3), 117.9 (Cp).
ethylene, R-olefin coordination becomes more facile with less
bulky methyl substituents on the aryl ring. With 1-hexene,
Keq(-95 °C) ≈ 7 L/mol was determined for 2d + C6H12
h
10d (R′′ t C4H9). Also, the relative difference between
ethylene and R-olefin binding is smaller in comparison to 2a:
Keq(1-hexene)/Keq(ethylene) ≈ 0.09.
Conclusions
The Pd(II) catalysts described here allow for the copoly-
merization of ethylene and R-olefins with methyl acrylate to
high molar mass polymers by a coordination-type polymeriza-
tion. Highly branched amorphous polymers are obtained. The
acrylate functionality is predominantly located in a unique
fashion at the ends of branches. By employing long chain
R-olefins as monomers, more linear segments can be introduced,
resulting in copolymers with lower branching than in the
ethylene acrylate copolymers and thus different properties.
Air- and temperature-stable palladium alkyl and chelate
compounds can conveniently be employed as well-defined
catalyst precursors. Systematic variation of the R-diimine ligand
revealed that reduction of the steric bulk of the substituents on
the aryl moieties results in higher methyl acrylate incorporation,
but at the same time molecular weight of the polymers is
lowered.
Low-temperature NMR studies provide a detailed picture of
the reaction mechanism. Migratory insertion of methyl acrylate
into a Pd-Me bond occurs regioselectively in a 2,1-mode. The
primary insertion product 6 rearranges to a six-membered chelate
complex 2 (eq 2). A corresponding rearrangement is thought
to occur in the copolymerization prior to the next insertion of
monomer and thus accounts for the incorporation of the ester
functionality at the ends of branches in the copolymers.
Displacement of the carbonyl oxygen donor in the MA chelates
2 by ethylene or R-olefins could only be observed at low
temperatures. Formation of analogous chelate compounds
during the copolymerization is believed to hinder monomer
coordination and thus to be responsible for the lower rates of
acrylate copolymerization reactions in comparison to ethylene
or R-olefin copolymerizations.
Acetonitrile Adducts. [(ArNdC(R)-C(R)dNAr)Pd(Me)(NCMe)]+
were prepared by the following general procedure in good yields
(>95%) using AgSbF6 or NaBAr′4. At room temperature, 5.34 mmol
of AgSbF6 was added to the acetonitrile solution of (ArNdC(R)-
C(R)dNAr)Pd(Me)(Cl) (5.34 mmol in 100 mL of CH3CN), resulting
in immediate precipitation of AgCl. This mixture was allowed to stir
overnight. AgCl was removed via filtration, and the solvent was
evaporated. The solid was dissolved in ca. 15 mL of CH2Cl2. Pentane
(120 mL) was subsequently added to precipitate the product. The
resulting solid was filtered, washed with 2 × 15 mL of pentane, and
dried in vacuo. Representative spectroscopic data for 3b (Ar t 2,6-
iPr2C6H3, R t Me) follows: 1H NMR (CD2Cl2, 250 MHz) δ 7.42-
7.28 (m, 6H; Haryl), 2.90 and 2.86 (septet, J ) 7 Hz, 2H each, CHMe2
and C′HMe2), 2.22 (s, 6H, NdC(Me)-C′(Me)dN), 1.77 (s, 3H; NCMe),
1.37, 1.33, 1.24 and 1.20 (d, J ) 7, 6H each; CHMeMe′ and
C′HMeMe′), 0.51 (s, 3H; PdMe). Anal. Calcd for (C32H46N3PdSbF6):
C, 46.3; H, 5.78; N, 5.23. Found: C, 46.13; H, 5.86; N, 5.38.
[(ArNdC(Me)-C(Me)dNAr)Pd(Me)(NCAr′′)](BAr′4) (4b; Ar t
2,6-iPr2C6H3, Ar′′ t 3,5-C6H3(CF3)2). To a mixture of 0.6717 g of
[(N∧N)PdMeCl] (1.196 mmol) and 1.068 g of NaBAr′4 (1.205 mmol)
was added ether (15 mL). 3,5-Bis(trifluoromethyl)benzonitrile (0.374
g, 1.564 mmol) was added via syringe. After being stirred for 4 h, the
reaction mixture was concentrated in vacuo to ca. 3 mL. The product
was precipitated by addition of hexane (25 mL). The supernatant was
decanted, and the precipitate was washed with hexane and dried in
vacuo briefly. The solid was redissolved in methylene chloride (5 mL),
and the resulting solution was cannula-filtered. Removal of solvent
and drying in vacuo yielded 1.69 g of orange powder (87%). 1H NMR
(CD2Cl2, 250 MHz) δ 8.23 (br s, 1H; Hp of C6H3(CF3)2), 7.56 (s
A mechanistic model was developed based on kinetic data
for the migratory insertion reactions and relative binding studies
for the comonomers. Migratory insertion of the electron-
deficient MA occurs much more rapidly than insertion of the
nonpolar olefins. However, this effect is overridden by the low
binding affinity of MA to the electrophilic cationic metal center,
resulting in predominant incorporation of the nonpolar olefin
at equal molar concentrations of the comonomers in the
copolymerization reaction. Extrapolation of the results of low-
temperature NMR experiments corresponds well with the
acrylate incorporation observed in the copolymer.
Experimental Section
General Considerations. All manipulations of air- and/or water-
sensitive compounds were performed using standard Schlenk tech-
niques. Argon and nitrogen were purified by passage through columns
of BASF R-3-11 catalyst (Chemalog) and 4 Å molecular sieves. Solid
organometallic compounds were transferred in an argon-filled Vacuum
Atmospheres drybox and, unless stated otherwise, were stored in the
drybox at room temperature. NMR spectra were recorded with a Varian
XL-400, Bruker AMX-300, Bruker WM-250, or Varian Gemini 2000
(300 MHz for 1H) spectrometer. 1H and 13C NMR chemical shifts were
referenced to residual 1H NMR signals and to the 13C NMR signals of
the deuterated solvents, respectively. NMR probe temperatures were
measured using an external anhydrous methanol sample. A (1°
deviation was assumed in error calculations. Errors in ∆Hq and ∆Sq
(35) Morse, P. M.; Spencer, M. D.; Wilson, S. R.; Girolami, G. S.
Organometallics 1994, 13, 1646-1655.
(36) Brookhart, M.; Grant, B.; Volpe, A. F., Jr. Organometallics 1992,
11, 3920-3922.
(37) Appleby, I. C. Chem. Ind. 1971, 120.

Pd-Catalyzed Copolymerization of Ethylene and R-Olefins
overlapping with BAr′4-signal, 2H; Ho of C6H3(CF3)2), 7.48-7.33 (m,
J. Am. Chem. Soc., Vol. 120, No. 5, 1998 897
0.66 (pentet, 2, J ) 5.76, PdCH2CH2CH2C(O)); 13C NMR (CD2Cl2,
100 MHz, room temperature) δ 183.4 (C(O)), 178.7 and 171.6 (NdC-
C′dN), 140.8 and 140.5 (Ar, Ar′: Cipso), 138.6 and 138.0 (Ar, Ar′:
Co), 129.3 and 128.3 (Ar, Ar′: Cp), 124.9 and 124.4 (Ar, Ar′: Cm),
54.9 (OMe), 35.8 and 30.3 (PdCH2CH2CH2C(O)), 29.5 and 29.2
(CHMe2, C′HMe2), 23.7 (PdCH2CH2CH2C(O)), 23.91, 23.86, 23.20 and
23.14 (CHMeMe′, C′HMeMe′), 21.6 and 19.9 (NdC(Me)-C′(Me)dN);
IR (CH2Cl2) 1643 cm-1 [ν(C(O))]. 7′b: 1H NMR (CD2Cl2, 400 MHz,
room temperature) δ 3.47 (s, 3, OMe), 2.54 (m, 1, CHMeC(O)), 2.19
and 2.18 (s, 3 each, NdC(Me)-C′(Me)dN), 1.02 (d, 3, J ) 7.23,
CHMeC(O)); 13C NMR (CD2Cl2, 100 MHz, room temperature) δ 194.5
(C(O)), 179.2 and 172.2 (NdC-C′dN), 55.6 (OMe), 44.3 (CHMeC-
(O)), 28.4 (PdCH2), 21.2 and 19.6 (NdC(Me)-C′(Me)dN), 18.1
(CHMeC(O)). 7b: 1H NMR (CD2Cl2, 400 MHz, room temperature) δ
0.26 (d, 3, PdCHMe). Anal. Calcd for (C65H61BF24N2O2Pd): C, 52.92;
H, 4.17; N, 1.90. Found: C, 52.91; H, 4.09; N, 1.68.
i
6H; C6H3 Pr2), 2.98 and 2.89 (septet, J ) 7 Hz, 2H each, CHMe2 and
C′HMe2), 2.28 and 2.26 (s, 3H each, NdC(Me)-C′(Me)dN), 1.36,
1.35, 1.26 and 1.23 (d, J ) 7, 6H each; CHMeMe′ and C′HMeMe′),
0.70 (s, 3H; PdMe). Anal. Calcd for (C70H58BF30N3Pd): C, 51.63;
H, 3.59; N, 2.58. Found: C, 51.59; H, 3.64; N, 2.51.
[(ArNdC(Me)-C(Me)dNAr)Pd(CH2)3C(O)OMe](BAr′4) (2d; Ar
t 2,6-Me2C6H3). Diethyl ether (3 mL) was added to a mixture of
0.1861 g of [(N∧N)PdMeCl] (0.414 mmol) and 0.3700 g of NaBAr′4
(0.417 mmol). The yellow suspension was stirred for 20 min, and then
methylene chloride (10 mL) was added, followed by 50 µL MA (0.6
mmol). After being stirred for 1.5 h, the resulting brown mixture was
concentrated in vacuo to ca. 3 mL. Addition of pentane (20 mL) yielded
a brown precipitate. The supernatant was decanted, and the precipitate
was washed with pentane and dried in vacuo briefly. The solid was
redissolved in methylene chloride (3 mL), and cannula filtration yielded
a clear bright red solution. Removal of solvent and drying in vacuo
gave 0.49 g of orange powder (87%), which consisted of a mixture of
2d (89%), 7′d (6%), and 7d (5%). 1H NMR (CDCl3, 250 MHz) 2d:
δ 7.16 and 7.07 (s, 3H each; C6H3Me2 and C′6H3Me2), 3.03 (s, 3H;
OMe), 2.34 (t, J ) 6 Hz, 2H; CH2C(O)), 2.14 and 2.12 (s, 6H each;
C6H3Me2 and C′6H3Me2), 2.09 and 2.04 (s, 3H each; NdC(Me)-
C′(Me)dN), 1.22 (t, J ) 6 Hz, 2H; PdCH2), 0.63 (pentet, J ) 6 Hz,
2H; PdCH2CH2CH2C(O)). IR (CH2Cl2) 1643 cm-1 (CdO). 7d: δ
3.71 (s, 3H; OMe), 0.23 (d, J ) 7 Hz, 3H; PdCHMe). 7′d: δ 3.47 (s;
OMe). Anal. Calcd for (C57H45BF24N2O2Pd): C, 50.22; H, 3.33; N,
2.05. Found: C, 50.29; H, 3.36; N, 2.04.
General Procedure for the Synthesis of Chelate Complexes. A
gastight microliter syringe was used to add 1.1 equiv of H2CdCHC-
(O)OMe to a mixture of 1 equiv of NaBAF and 1 equiv of
(ArNdC(R)-C(R)dNAr)PdMeCl suspended in 25 mL of Et2O. The
sides of the Schlenk flask were rinsed with an additional 25 mL of
Et2O, and the reaction mixture was stirred for 1-2 days at rt. Sodium
chloride was removed from the reaction mixture via filtration, yielding
a clear orange solution. The Et2O was removed in vacuo, and the
product was washed with hexane and dried in vacuo.
[(ArNdC(An)-C(An)dNAr)Pd(CH2)3C(O)OMe](BAr′4) (2c; Ar
t 2,6-(i-Pr)2C6H3). This complex was synthesized according to the
above general procedure using (ArNdC(An)-C(An)dNAr)PdMeCl
(744 mg, 1.13 mmol), NaBAF (1.00 g, 1.13 mmol), and MA (112 µL,
1.1 equiv). The reaction mixture was stirred for 2 days, and the product
was recrystallized from CH2Cl2 at -30 °C to give 600 mg (33.8%, 2
crops) of a mixture of 2c (85%), 7′c (8%), 7′′c (6%) {PdCH2CH2C-
(O)OMe}, and 7c(Me) (1%), according to 1H NMR spectroscopy. 2c:
1H NMR (CD2Cl2, 400 MHz, room temperature) δ 8.17 (d, 1, J )
8.37, An: Hp), 8.15 (d, 1, J ) 3.49, An′: H′p), 7.62-7.40 (m, 8, An:
Hm, An′: Hm; Ar: Hm, Hp; Ar′: H′m, H′p), 7.08 (d, 1, J ) 7.19, An:
Ho), 6.60 (d, 1, J ) 7.44, An′: H′o), 3.37 (septet, 2, J ) 6.79, CHMe2),
3.33 (septet, 2, J ) 6.86, C′HMe2), 3.23 (s, 3, OMe), 2.55 (t, 2, J )
5.93, CH2C(O)), 1.79 (t, 2, J ) 5.66, PdCH2), 1.45, 1.42, 1.13 and
1.02 (d, 6 each, J ) 6.79-6.90, CHMeMe′, C′HMeMe′), 0.80 (pentet,
2, J ) 5.82, PdCH2CH2CH2C(O)); 13C NMR (CD2Cl2, 100 MHz, room
temperature) δ 183.5 (C(O)), 175.3 and 168.7 (NdC-C′dN), 145.9
(An: quaternary C), 141.3 and 140.5 (Ar, Ar′: Cipso), 139.7 and 138.4
(Ar, Ar′: Co), 133.3 and 132.6 (An: CH), 131.9 (An: quaternary C),
129.8, 129.7, 129.6 and 128.5 (Ar, Ar′: Cp; An: CH), 126.44 and 125.8
(An: quaternary C), 126.4 and 125.6 (An: CH), 125.5 and 124.6 (Ar,
Ar′: Cm), 55.0 (OMe), 35.9 and 31.3 (PdCH2CH2CH2C(O)), 29.7 and
29.4 (CHMe2, C′HMe2), 24.1 (PdCH2CH2CH2C(O)), 24.1, 23.8, 23.32
and 23.27 (CHMeMe′, C′HMeMe′); IR (CH2Cl2) 1644 cm-1 [ν(C(O))].
7′c: 1H NMR (CD2Cl2, 400 MHz, room temperature) δ 3.64 (s, 3,
OMe), 2.70 (m, 1, CHMeC(O)); 13C NMR (CD2Cl2, 100 MHz, room
temperature) δ 192.8 (C(O)). 7′′c: 1H NMR (CD2Cl2, 400 MHz, room
temperature) δ 3.67 (s, 3, OMe), 2.46 (t, 2, J ) 6.99, CH2C(O)), 1.72
(t, 2, J ) 7.04, PdCH2). 7c: 1H NMR (CD2Cl2, 400 MHz, room
[(ArNdC(H)-C(H)dNAr)Pd(CH2)3C(O)OMe](BAr′4) (2a; Ar t
2,6-(i-Pr)2C6H3). This complex was synthesized according to the above
general procedure using (ArNdC(H)-C(H)dNAr)PdMeCl (937 mg,
1.76 mmol), NaBAF (1.56 g, 1.75 mmol), and MA (175 µL, 1.1 equiv).
The resulting orange powder (2.44 g, 96.0%) consisted of a mixture of
2a (91%), 7′a (5%), and 7a (4%), according to 1H NMR spectroscopy.
1
2a: H NMR (CD2Cl2, 400 MHz, room temperature) δ 8.31 and 8.26
(s, 1 each, NdC(H)-C′(H)dN), 7.5-7.2 (m, 6, Haryl), 3.17 (s, 3, OMe),
3.14 and 3.11 (septet, 2 each, CHMe2 and C′HMe2), 2.48 (t, 2, J )
5.8, CH2C(O)), 1.75 (t, 2, J ) 5.8, PdCH2), 1.38, 1.32, 1.25, and 1.22
(d, 6 each, J ) 6.8, CHMeMe′ and C′HMeMe′), 0.73 (pentet, 2, J )
5.8, PdCH2CH2CH2C(O)); 13C NMR (CD2Cl2, 100 MHz, room tem-
temperature)
δ
0.44 (d, 3, PdCHMe). Anal. Calcd for
(C73H61BF24N2O2Pd): C, 55.80; H, 3.91; N, 1.78. Found: C, 55.76;
H, 3.82; N, 1.62.
General Procedure for Variable Temperature NMR Experi-
ments. In a drybox under an argon atmosphere, the palladium complex
(approximately 0.01 mmol) was weighed into an NMR tube. The tube
was then capped with a septum, removed from the drybox, and cooled
to -78 °C. CD2Cl2 (0.7 µL) was then added to the NMR tube via
gastight syringe, and the septum was wrapped with Parafilm. The tube
was shaken very briefly in order to dissolve the palladium complex.
After acquiring a spectrum at low temperature, gaseous or liquid olefins
and other reagents were added to the solution at -78 °C (-100 °C in
reactions involving MA added as a CD2Cl2 solution) via gastight syringe
and were dissolved in the solution by briefly shaking the NMR tube.
perature) δ 183.9 (C(O)), 167.1 (JCH ) 181.4, NdC(H)), 160.7 (JCH
)
181.3, NdC′(H)), 142.9 and 142.4 (Ar, Ar′: Cipso), 139.7 and 138.7
(Ar, Ar′: Co), 129.8 and 129.0 (Ar, Ar′: Cp), 124.6 and 124.1 (Ar,
Ar′: Cm), 55.2 (OMe), 35.9 and 32.3 (PdCH2CH2CH2C(O)), 29.3 and
29.1 (CHMe2, C′HMe2), 23.8 (PdCH2CH2CH2C(O)), 24.5, 23.9, 23.2,
and 22.5 (CHMeMe′, C′HMeMe′); IR (CH2Cl2) 1640 cm-1 [ν(C(O))].
7′a: 13C NMR (CD2Cl2, 100 MHz, room temperature) δ 193.2 (C(O)).
Spectral data for 7a are reported below. Anal. Calcd for
(C63H57BF24N2O2Pd): C, 52.28; H, 3.97; N, 1.94. Found: C, 52.08;
H, 3.75; N, 1.61.
[(ArNdC(Me)-C(Me)dNAr)Pd(CH2)3C(O)OMe](BAr′4) (2b; Ar
t 2,6-(i-Pr)2C6H3). This complex was synthesized according to the
above general procedure using (ArNdC(Me)-C(Me)dNAr)PdMeCl
(634 mg, 1.13 mmol), NaBAF (1.00 g, 1.13 mmol), and MA (112 µL,
1.1 equiv). The reaction mixture was stirred for 2 days, and the product
was recrystallized from CH2Cl2 at -30 °C to give 956 mg of orange
crystals (57.3%, 2 crops). The crystals consisted of a mixture of 2b
(87%), 7′b (11.5%), and 7b (1.5%), according to 1H NMR spectroscopy.
2b: 1H NMR (CD2Cl2, 400 MHz, room temperature) δ 7.43-7.26 (m,
6, Haryl), 3.03 (s, 3, OMe), 2.95 (septet, 2, J ) 6.79, CHMe2), 2.93
(septet, 2, J ) 6.83, C′HMe2), 2.39 (t, 2, J ) 5.86, CH2C(O)), 2.22
and 2.20 (NdC(Me)-C′(Me)dN), 1.41 (t, 2, J ) 5.74, PdCH2), 1.37,
1.30, 1.25 and 1.21 (s, 6 each, J ) 6.80-6.94, CHMeMe′, C′HMeMe′),
1
The tube was then transferred to the cold NMR probe, and H NMR
spectra were acquired (delay times g20 s, except for MA-insertion
kinetics). The molarity of the BAr′4- counterion was calculated from
the amount of palladium complex employed and used as an internal
standard.
Methyl Acrylate Chelate Formation and Rearrangement. One
equiv of MA was added to a 0.0198 M solution of [(ArNdC(H)-
C(H)dNAr)PdMe(OEt2)]BAF in CD2Cl2 at -78 °C, and the tube was
transferred to the precooled NMR probe. After 14.25 min at -80 °C,
approximately 80% of the ether adduct had been converted to the olefin
complex 5a. Two sets of bound olefin resonances were observed in a
86:14 ratio. This observation is consistent with the existence of two

898 J. Am. Chem. Soc., Vol. 120, No. 5, 1998
Mecking et al.
different rotamers of the olefin complex. Insertion of MA into the
Pd-Me bond occurred with predominantly 2,1 regiochemistry to give
the four-membered chelate 6a at -80 °C (t1/2 ∼ 2.0 h). The resonances
for the major rotamer of the olefin complex disappeared before those
of the minor rotamer. Much slower conversion of 6a to the five-
membered chelate 7a also began at -80 °C. Upon warming to -60
°C, complete and selective formation of 7a occurred in less than 4 h.
The five-membered chelate was relatively stable at temperatures below
-50 °C; however, upon warming to -20 °C, rearrangement to the six-
membered chelate 2a was observed. NMR spectral data for 5a, 6a,
and 7a follow. Spectral data for 2a are identical with that of the isolated
chelate complex (vide supra).
[(ArNdC(H)-C(H)dNAr)Pd(Me)(H2CdCHC(O)OMe)]BAF (5a;
Ar t 2,6-(i-Pr)2C6H3). 1H NMR (CD2Cl2, -80 °C, 400 MHz) major
rotamer: δ 8.45 and 8.32 (s, 1 each, NdC(H)-C′(H)dN), 7.5-7.1
(m, 6, Haryl), 5.14 (d, J ) 15.2, HH′Cd), 4.96 (dd, J ) 14.9, 8.6,
dCHC(O)), 4.63 (d, J ) 8.5, HH′Cd), 3.68 (s, 3, OMe), 3.03, 2.90,
2.80 and 2.67 (septet, 1 each, CHMe2, C′HMe2, C′′HMe2, C′′′HMe2),
1.5-1.0 (doublets, 24, CHMe2), 0.61 (s, 3, PdMe); minor rotamer: δ
8.25 and 8.18 (s, 1 each, NdC(H)-C′(H)dN), 5.25 (d, 1, HH′Cd),
4.78 (dd, 1, dCHC(O)), 4.58 (d, 1, HH′Cd), 3.63 (OMe).
[(ArNdC(H)-C(H)dNAr)Pd(CH2CH2C(O)OMe)]BAF, were observed.
R ) Me: The above procedure was followed with analogous results,
e.g., resonances for the formation of a substituted six-membered chelate
complex [(ArNdC(Me)-C(Me)dNAr)Pd(CHR′′CH2CH2C(O)OMe)]-
BAF were observed following complete ethylene consumption [3.03
(s, OMe), 3.12, 2.96, 2.89, 2.83 (septets, CHMe2, C′HMe2, C′′HMe2
and C′′′HMe2), 2.23 and 2.19 (s, NdC(Me)-C′(Me)dN)]. Again, the
large upfield shift of the methoxy resonance is diagnostic for the
formation of the six-membered chelate complex. The observation of
four isopropyl methine resonances (vs two isopropyl methine resonances
in the unsubstituted six-membered chelate complex) reflects the
asymmetry introduced in the molecule due to the introduction of the
R′′ substituent on CR of the chelate ring and further supports the
proposed structure.
Insertion Rate of MA. Following the general procedure given
above, MA was added to the ether adduct 1a, and the sample was
transferred to the probe cooled to -95 °C. To achieve complete
conversion to 5a, the sample was kept at -85 °C for ca. 30 min. After
warming up to the reaction temperature, disappearance of the methyl
signal of 5 was monitored.
Equilibria [(N∧N)PdMe(L)]+ + L′ h [(N∧N)PdMe(L′)]+ + L.
The ligands L and L′ were added to a CD2Cl2 solution of the ether-
adducts 1 according to the above general procedure. In reactions
involving nitriles, optionally the nitrile complexes 3 or 4 were employed
directly instead of 1. Relative concentrations were determined by
integration of the Pd-Me signals of the two complexes and suitable
signals of free L and L′. Spectroscopic data for the ethylene (8a-b)
and propylene complexes has been reported.14
[(ArNdC(H)-C(H)dNAr)Pd(CHEtC(O)OMe)]BAF (6a; Ar t
2,6-(i-Pr)2C6H3). 1H NMR (CD2Cl2, 400 MHz, -60 °C) δ 8.25 and
8.22 (NdC(H)-C′(H)dN), 7.5-7.2 (m, 6, Haryl), 3.74 (s, 3, OMe),
3.55, 3.27, 3.08 and 2.76 (m, 1 each, CHMe2, C′HMe2, C′′HMe2,
C′′′HMe2), 2.62 (dd, J ) 10.8, 2.9, CHEt), 1.4-1.0 (doublets, 24,
CHMe2), 0.79 and -0.49 (m, 1 each, CH(CHH′Me)), 0.71 (t, 3, J )
6.6, CH(CHH′Me)).
[(ArNdC(H)-C(H)dNAr)PdMe(p-CH2)CHC6H4OMe)]-
(BAr′4) (Ar t 2,6-iPr2C6H3). 1H NMR (CD2Cl2, 300 MHz, -85 °C)
δ 8.40 and 8.35 (s, 1H each, NdC(H)-C′(H)dN), 7.44-7.14 (m, 8H;
[(ArNdC(H)-C(H)dNAr)Pd(CHMeCH2C(O)OMe)]BAF (7a;
Ar t 2,6-(i-Pr)2C6H3). 1H NMR (CD2Cl2, 400 MHz, -60 °C) δ 8.24
and 8.21 (NdC(H)-C′(H)dN), 7.4-7.2 (m, 6, Haryl), 3.59 (s, 3, OMe),
3.47, 3.32, 2.98 and 2.81 (septet, 1 each, CHMe2, C′HMe2, C′′HMe2,
C′′′HMe2), 3.08 (dd, 1, J ) 18.4, 7.3, CHH′C(O)), 1.74 (pentet, 1, J )
6.9, PdCHMe), 1.60 (d, 1, J ) 18.6, CHH′C(O)), 1.34 (d, 6, J ) 5.6,
C′HMeMe′ and C′′′HMeMe′), 1.32 (d, 3, J ) 6.2, CHMeMe′), 1.24 (d,
3, J ) 6.8, C′′HMeMe′), 1.18 (d, 6, J ) 6.8, C′HMeMe′ and
C′′HMeMe′), 1.15 (d, 3, J ) 6.8, C′′′HMeMe′), 1.08 (d, 3, CHMeMe′),
0.35 (d, 3, J ) 6.9, PdCHMe); 13C NMR (CD2Cl2, 100 MHz, -80 °C)
δ 190.5 (C(O)), 166.1 (JCH ) 181, NdC(H)), 160.7 (JCH ) 181,
N)C′(H)), 142.8 and 141.6 (Ar, Ar′: Cipso), 139.0, 138.6, 138.2 and
137.7 (Ar: Co, Co′ and Ar′: Co, Co′), 128.8 and 128.2 (Ar, Ar′: Cp),
124.1, 123.54, 123.48, 123.4 (Ar: Cm, Cm′ and Ar′: Cm, Cm′), 55.5
(OMe), 45.1 (CH2C(O)), 35.6 (PdCHMe), 28.8, 28.5, 28.1 and 27.8
(CHMe2, C′HMe2, C′′HMe2, C′′′HMe2), 25.6, 24.2, 23.1, 23.0, 22.7,
22.3, 21.9, 21.3, and 21.3 (CHMeMe′, C′HMeMe′, C′′HMeMe′,
C′′′HMeMe′ and PdCHMe).
Reaction of [(ArNdC(R)-C(R)dNAr)PdMe(OEt2)]BAF [R )
H (1a), Me (1b)] with Ethylene and Methyl Acrylate. R ) H. A
solution of [(ArNdC(H)-C(H)dNAr)PdMe(OEt2)]BAF (21.5 mg,
0.0150 mmol) in 700 µL of CD2Cl2 was prepared at -78 °C. Ethylene
(5 equiv) was added via gastight syringe, and the tube was shaken
briefly to dissolve the ethylene. Methyl acrylate (5 equiv) was then
added to the solution, also via gastight microliter syringe, and the tube
was shaken briefly again. The tube was transferred to the NMR probe,
which was precooled to -80 °C. Resonances consistent with the
formation of the ethylene adduct [(ArNdC(H)-C(H)dNAr)PdMe-
(H2CdCH2)]BAF14 were observed. The solution was warmed, and
ethylene insertion wasd monitored at -40 to -20 °C. The consumption
of 1 equiv of methyl acrylate occurred as the last equiv of ethylene
disappeared, and resonances consistent with the formation of a
substituted six-membered chelate complex [(ArNdC(H)-C(H)dNAr)-
Pd-(CHR′′CH2CH2C(O)OMe)]-BAF were observed [8.30 and 8.29
(NdC(H)-C′(H)dN), 3.17 (OMe)]. The large upfield shift of the
methoxy resonance is particularly diagnostic for formation of the six-
membered chelate complex in these systems. The substituted six-
membered chelate complex was observed at -20 °C and initially upon
warming to room temperature. After 2 h at room temperature,
decomposition of the substituted six-membered chelate complex had
begun. After 24 h at room temperature, an additional 0.5 equiv of
MA had been consumed and triplets at 2.42 and 1.66 ppm, consistent
with the formation of the unsubstituted five-membered chelate complex
i
C6H3 Pr2 and C6H4OMe), 6.80 (d, J ) 8 Hz, 2H; C6H4OMe), 6.33 (dd,
J ) 16 Hz, J ) 8 Hz, 1H; -CHd), 4.61 (d, J ) 16 Hz, 1H;
-CHdCHcisH), 3.99 (d, J ) 8 Hz, 1H; -CHdCHHtrans), 3.71 (s, 3H,
OMe), 3.08-2.80 (m, 3H; CHMe2), 2.80-2.64 (m, 1H; C′HMe2),
1.54-0.97 (m, 24H, CHMe2), 0.03 (s, 3H; PdMe).
[(ArNdC(H)-C(H)dNAr)PdMe(CH2dCHnC4H9](BAr′4) (Ar t
2,6-iPr2C6H3). 1H NMR (CD2Cl2, 300 MHz, -84 °C) δ 8.40 and 8.24
i
(s, 1H each, NdC(H)-C′(H)dN), 7.41-7.21 (m, 6H; C6H3 Pr2), 5.25
(br, 1H; -CHd), 4.32 (d, J ) 6 Hz, 1H; -CHdCHtransH), 4.17 (br,
1H; -CHdCHHcis), 3.05-2.75 (m, 3H; CHMe2), 2.75-2.53 (m, 1H;
C′HMe2), 0.43 (s, 3H; PdMe).
n
Equilibria 2 + CH2dCHR′′ h 10 (R′′ t H, Me, C4H9). The
general procedure for NMR experiments described above was em-
ployed. CD2Cl2 was added at room temperature to the NMR tube
containing 0.01 mmol of 2, and the tube was weighed to precisely
determine the amount of solvent. The ratio 2/10 was determined by
integration of their OMe- or one of the PdCH2CH2CH2-signals and the
concentration of free olefin was determined from the integral of the
-
olefinic protons vs the BAr′4 counterion.
[(ArNdC(H)-C(H)dNAr)Pd(H2CdCH2)(CH2CH2CH2C(O)-
OMe)]BAF (10a). 1H NMR (CD2Cl2, 300 MHz, 182 K) δ 8.30 and
8.29 (s, 1 each, NdC(H)-C′(H)dN), 7.38-7.24 (m, 6, Haryl), 3.72 (s,
3, OMe), 3.43 (br s, 4, H2CdCH2), 3.10 (m, 2, CHMe2), 2.70 (m, 2,
C′′HMe2), 2.20 (m, 2, CH2C(O)), 1.25, 1.16, 1.09 and 1.07 (d, 6 each,
J ) 7, CHMeMe′, C′HMeMe′), 1.20 (PdCH2 (obscurred by CHMeMe′
peaks, observed by H,H-COSY)), 0.56 (m, 2, PdCH2CH2CH2C(O));
13C NMR (CD2Cl2, 100 MHz, -80 °C) δ 178.9 (C(O)), 162.7 (JCH
)
179, NdC), 162.5 (JCH ) 179, NdC′), 141.3 and 140.5 (Ar, Ar′: Cipso),
138.5 and 138.1 (Ar, Ar′: Co), 128.5 and 128.3 (Ar, Ar′: Cp), 124.1
and 124.0 (Ar, Ar′: Cm), 122.9 (JCH ) 159.3, free H2C)CH2), 70.2
(JCH ) 158.6, bound H2CdCH2), 53.0 (OMe), 36.5, 33.0 and 22.6
(PdCH2CH2CH2C(O)), 27.8 (CHMe2, C′HMe2), 25.6, 25.3, 22.1 and
21.4 (CHMeMe′, C′HMeMe′).
[(ArNdC(Me)-C(Me)dNAr)Pd(H2CdCH2)(CH2CH2CH2C(O)-
OMe)]BAF (10b). Even at low temperature and in the presence of a
large excess of ethylene, this complex could only be observed in the
presence of at least an equimolar amount of the corresponding six-
1
membered chelate: H NMR (CD2Cl2, 300 MHz, 172 K): δ 7.35-
7.19 (m, 6, Haryl), 4.31 (br s, 4, H2CdCH2), 3.45 (s, 3, OMe), 2.73-
2.54 (m, 4, CHMe2), 2.38 and 2.22 (s, 3 each, NdC(Me)-C′(Me)dN),

Pd-Catalyzed Copolymerization of Ethylene and R-Olefins
J. Am. Chem. Soc., Vol. 120, No. 5, 1998 899
1.64 (m, 2, CH2C(O)), 1.02 (d, 6, J ) 6, CHMeMe′′). From the
available H,H-COSY data, the remaining PdCH2CH2CH2C(O)- and
CHMe-signals could not be unambiguously assigned, due to the
presence of the six-membered chelate 2b.
[(ArNdC(An)-C(An)dNAr)Pd(H2CdCH2)(CH2CH2CH2C(O)-
OMe)]BAF (10c). 1H NMR (CD2Cl2, 300 MHz, 178 K): δ 8.06 and
8.02 (d, J ) 8, 1 each, An and An′: Hp and H′p), 7.50-7.38 (m, 8, An
and An′: H′m and Hm, Ar: Hm and Hp), 6.48 (d, J ) 7, 2, An and An′:
Ho and H′o), 4.56 (br s, 4, H2CdCH2), 3.45 (s, 3, OMe), 2.99 and 2.91
(m, 2 each, CHMe2 and C′HMe2), 1.77 (m, 2, CH2C(O)), 1.29, 1.27,
0.82 and 0.77 (d, J ) 6-7, 6 each, CHMeMe′, C′HMeMe′). H,H-
COSY reveals that the remaining PdCH2CH2CH2C(O)-signals are
obscurred by the CHMe-signals at 1.2 ppm.
or propylene, constant pressure was applied by continuously feeding
the gaseous olefin and the contents of the reactor were vigorously
stirred. After the specified reaction time, the gas was vented. Volatiles
were removed from the reaction mixture in vacuo, and the polymer
was dried under vacuum overnight.
The volatile fractions distilled from the reaction mixtures upon
isolation of the polymer according to the above procedures were
analyzed for low molecular weight products by gas chromatography
in representative runs.
Copolymer Spectral Data. In addition to the signals of the methyl,
methylene and methine groups originating from ethylene or the
R-olefin,14 the 1H and 13C NMR spectra of the copolymers exhibit
characteristic resonances due to the functionalized comonomer. Spec-
troscopic data and graphic depictions of NMR spectra have been
reported for the ethylene- and propylene-copolymers.15 The IR-spectra
display the carbonyl band of the functional groups originating from
the comonomer. Ethylene-MA copolymer: 1H NMR (CDCl3, 400
MHz) δ 3.64 (s, OCH3), 2.28 (t, J ) 7, CH2C(O)), 1.58 (m, CH2CH2C-
(O)); 13C NMR (C6D6, 100 MHz) δ 176 (C(O)), 50.9 (OCH3); IR
[(ArNdC(H)-C(H)dNAr)Pd{(CH2)3C(O)OMe}(CH2dCHCH3)]-
(BAr′4) (Ar t 2,6-iPr2C6H3; 10a (R′′ t Me)). 1H NMR (CD2Cl2,
ca. 6 weight % propene present, 300 MHz, -94 °C) δ 3.61 (s, 3H;
OMe).
[(ArNdC(H)-C(H)dNAr)Pd{(CH2)3C(O)OMe}(CH2dCHnC4H9)]-
(BAr′4) (Ar t 2,6-iPr2C6H3; 10a (R′′ t n-C4H9)). 1H NMR (CD2Cl2,
ca. 12 vol % 1-hexene present, 300 MHz, -88 °C) δ 8.35 and 8.27 (s,
1H each; NdC(H)-C′(H)dN), 3.57 (s, 3H; OMe), 2.57 (m, 1H;
1
(film): 1744 cm-1 [ν(C(O))]. Propylene-MA copolymer: H NMR
(CDCl3, 250 MHz) δ 3.64 (s, OCH3), 2.3 (m, CH2C(O)); 13C NMR
(CDCl3, 62 MHz) δ 174.5 (C(O)), 51.4 (OCH3); IR (film): 1747 cm-1
[ν(C(O))]. (1-Hexene)-MA copolymer: 1H NMR (CDCl3, 250 MHz)
δ 3.64 (s, OCH3), 2.28 (t, J ) 7 Hz, CH2C(O)), 1.60 (m, CH2CH2C-
(O)). 13C NMR (CDCl3, 75 MHz) δ 174.2 (C(O)), 51.4 (OCH3). (1-
CHMe2).
[(ArNdC(Me)-C(Me)dNAr)Pd{(CH2)3C(O)OMe}-
(CH2dCH2)](BAr′4) (Ar t 2,6-Me2C6H3; 10d (R′′ t H)). 1H NMR
(CD2Cl2, 300 MHz, -85 °C) δ 7.16 and 7.14 (s, 3H each; C6H3Me2
and C′6H3Me2, 4.09 (s, 4H; H2CdCH2), 3.53 (s, 3H; OMe), 2.27 (s,
3H; NdC(Me)-), 2.13 (s, 9H; C6H3Me2 and NdC′(Me)-), 2.06 (s, 6H;
C′6H3Me2), 1.61 (t, J ) 6 Hz, 2H; CH2C(O)), 0.89 (pentet, J ) 6 Hz,
2H; PdCH2CH2CH2C(O)), 0.76 (t, J ) 6 Hz, 2H; PdCH2).
1
Dodecene)-MA copolymer: H NMR (CDCl3, 250 MHz) δ 3.64 (s,
OCH3), 2.28 (t, J ) 7 Hz, CH2C(O)), 1.58 (m, CH2CH2C(O)). 13C
NMR (CDCl3, 75 MHz) δ 174.6 and 174.3 (C(O)), 51.4 (OCH3).
Ethylene Solubility. The Parr reactor described above (mass:
5550.1 g) was charged with 100 mL of solvent under a nitrogen
atmosphere and weighed. It was then pressurized with ethylene and
stirred under constant pressure. After equilibration, the reactor was
weighed again. The ethylene pressure was increased, and the procedure
was repeated (e.g., 2, 4, 6, 8, 11, 20 atmg). As the nitrogen atmosphere
was not expelled prior to pressurization (to avoid losses of solvent),
the pressure reading refers directly to ethylene partial pressure. To
account for the mass of ethylene in the gas-phase, the solvent was
replaced by glass beads of equal volume, and the experiment was
repeated. The difference in ethylene uptake yields the amount of
ethylene dissolved in the liquid phase for each pressure. This method
implies some approximations, especially the assumption of constant
volume of the liquid-phase results in significant errors at high pressures
(g40 atm). However, it is sufficiently accurate for the purposes
employed. In the range up to 11 atmg, a solubility in methylene
chloride of 0.18 mol/L atm was found vs 0.16 mol/L atm for neat methyl
acrylate. Solubility in a 1:1 mixture of the two compounds was found
to be intermediate, as expected.
(ArNdC(Me)-C(Me)dNAr)Pd{(CH2)3C(O)OMe}(CH2dCH-
nC4H9)](BAr′4) (Ar t 2,6-Me2C6H3; 10d (R′′ t n-C4H9)). 1H NMR
(CD2Cl2, 300 MHz, -95 °C) δ 3.48 (s, 3H; OMe).
General Procedures for Polymerization Reactions. (a) Copoly-
merizations of Ethylene at Ambient Pressure. In a 100 mL Schlenk
flask, 0.1 mmol of palladium catalyst and 5 mL of methyl acrylate
were dissolved in 40 mL of CH2Cl2. The flask was connected to a
Schlenk line, and the flask was then briefly evacuated and refilled with
ethylene from the Schlenk line. This was stirred at room temperature
under 1 atm of ethylene for the specified reaction time. Volatiles were
removed under vacuum. The copolymer was vacuum-dried. (b)
Copolymerizations of Liquid r-Olefins. To a methylene chloride
solution of 0.05 mmol of the catalyst precursor in a Schlenk tube, a
mixture of weighed amounts of the R-olefin (10-20 mL) and methyl
acrylate (5 mL) was transferred via cannula under a nitrogen atmosphere
(total volume of the liquid phase: 50 mL). After stirring for the
specified reaction times, volatiles were removed rapidly in vacuo. For
volatile R-olefin monomers (hexene) the polymer was directly obtained.
For nonvolatile R-olefins (dodecene), the remaining mixture was poured
into 100 mL of methanol under rapid stirring. The supernatant was
decanted from the precipitated polymer, which was washed twice with
methanol. The polymers were dried in vacuo. (c) Polymerizations
at Elevated Pressure. Reactions were carried out in a mechanically
stirred 300 mL Parr reactor, equipped with an electric heating mantle
Acknowledgment. This work was supported by the National
Science Foundation (CHE-9412095) and by DuPont. L.K.J.
thanks the NSF for a postdoctoral fellowship and S.M. thanks
the Alexander von Humboldt Foundation for a Feodor-Lynen-
Fellowship. We thank J. M. DeSimone’s group for providing
GPC analyses and Yueli Wang, Carole Urbston, and Adrian
Huang for excellent technical assistance.
controlled by a thermocouple dipping into the reaction mixture.
A
solution of 0.1 mmol of catalyst precursor in methylene chloride,
containing the functionalized comonomer (5-50 mL, total volume of
the liquid phase: 100 mL), was transferred via cannula to the reactor
under a nitrogen atmosphere. After repeatedly flushing with ethylene
JA964144I