Journal of the American Chemical Society
Communication
REFERENCES
■
(
1) (a) Mecking, S.; Johnson, L. K.; Wang, L.; Brookhart, M. J. Am.
Chem. Soc. 1998, 120, 888. (b) Johnson, L. K.; Mecking, S.; Brookhart,
M. J. Am. Chem. Soc. 1996, 118, 267.
(
2) Drent, E.; van Dijk, R.; van Ginkel, R.; van Oort, B.; Pugh, R. I.
Chem. Commun. 2002, 744.
3) (a) Carrow, B. P.; Nozaki, K. Macromolecules 2014, 47, 2541.
b) Nakamura, A.; Anselment, T. M. J.; Claverie, J. P.; Goodall, B.;
(
(
Jordan, R. F.; Mecking, S.; Rieger, B.; Sen, A.; van Leeuwen, P. W. N.
M.; Nozaki, K. Acc. Chem. Res. 2013, 46, 1438. (c) Nakamura, A.; Ito,
S.; Nozaki, K. Chem. Rev. 2009, 109, 5215. (d) Chen, E. Y. -X. Chem.
Rev. 2009, 109, 5157. (e) Berkefeld, A.; Mecking, S. Angew. Chem., Int.
Ed. 2008, 47, 2538. (f) Ittel, S. D.; Johnson, L. K.; Brookhart, M.
Chem. Rev. 2000, 100, 1169.
Figure 3. Observed rate constants of elimination of 11-dmso and 12-
(4) (a) Ota, Y.; Ito, S.; Kuroda, J.; Okumura, Y.; Nozaki, K. J. Am.
−1
dmso ([Pd] = 0.025 mol L , C D Cl ). Data at 1000 s after addition
2
2
4
Chem. Soc. 2014, 136, 11898. (b) Lanzinger, D.; Giuman, M. M.;
Anselment, T. M. J.; Rieger, B. ACS Macro Lett. 2014, 3, 931.
of reagents to the NMR tube is taken as the initial concentration, [c0].
(
c) Leicht, H.; Go
Ed. 2013, 52, 3963. (d) Carrow, B. P.; Nozaki, K. J. Am. Chem. Soc.
012, 134, 8802. (e) Piche, L.; Daigle, J.-C.; Rehse, G.; Claverie, J. P.
̈
ttker-Schnetmann, I.; Mecking, S. Angew. Chem., Int.
2
qualitatively with the observed considerably higher molecular
weights of AA copolymers and the minor portion of AA-derived
Chem.Eur. J. 2012, 18, 3277. (f) Ito, S.; Kanazawa, M.; Munakata,
K.; Kuoda, J.; Okumura, Y.; Nozaki, K. J. Am. Chem. Soc. 2011, 133,
1
1
232. (g) Ru
32, 17690. (h) Ito, S.; Munakata, K.; Nakamura, A.; Nozaki, K. J. Am.
nzi, T.;
ttker-Schnetmann, I.; Mecking, S. J. Am. Chem. Soc. 2009, 131, 422.
j) Kochi, T.; Noda, S.; Yoshimura, K.; Nozaki, K. J. Am. Chem. Soc.
007, 129, 8948. (k) Luo, S.; Vela, J.; Lief, G. R.; Jordan, R. F. J. Am.
̈
̈
nzi, T.; Frohlich, D.; Mecking, S. J. Am. Chem. Soc. 2010,
end groups. Studies of the insertion of E into 11-dmso (k ′)
E
and 12-dmso (k ″) at 15 °C showed that insertion into the
E
−4
−1
Chem. Soc. 2009, 131, 14606. (i) Guironnet, D.; Roesle, P.; Ru
Go
(
2
̈
primary alkyl-Pd (k ″ = 3 × 10 s ) is ca. 4-fold faster than
E
̈
−5
−1
into the secondary alkyl-Pd (k ′ = 9 × 10 s ).
E
In summary, our findings show that the concept of a second
rapid intramolecular insertion can help to overcome
fundamental issues of the insertion polymerization of
electron-poor polar monomers. The product of polar monomer
Chem. Soc. 2007, 129, 8946. (l) Weng, W.; Shen, Z.; Jordan, R. F. J.
Am. Chem. Soc. 2007, 129, 15450.
(5) (a) Neuwald, B.; Caporaso, L.; Cavallo, L.; Mecking, S. J. Am.
Chem. Soc. 2013, 135, 1026. (b) Friedberger, T.; Wucher, P.; Mecking,
S. J. Am. Chem. Soc. 2012, 134, 1010. (c) Guironnet, D.; Caporaso, L.;
Neuwald, B.; Gottker-Schnetmann, I.; Cavallo, L.; Mecking, S. J. Am.
̈
Chem. Soc. 2010, 132, 4418. (d) Nozaki, K.; Kusumoto, S.; Noda, S.;
Kochi, T.; Chung, L. W.; Morokuma, K. J. Am. Chem. Soc. 2010, 132,
(2,1-) insertion, which is usually less reactive for chain growth
but prone to β-H elimination and hereby limits molecular
weights, is rapidly reacted before chain transfer occurs. At the
same time, conformational constraints force this intramolecular
insertion to occur in the electronically less favored 1,2-mode.
This yields a primary alkyl, which is reactive for further chain
growth and disfavors β-H elimination. This is reflected by
significantly higher molecular weights. The resulting micro-
structures resemble linear ethylene−maleic anhydride copoly-
mers. They are not accessible via maleic anhydride copoly-
merization due to poor incorporations. The anhydride repeat
units render these novel polyethylenes reactive for various
desirable post-polymerization reactions.
1
6030. (e) Noda, S.; Nakamura, A.; Kochi, T.; Chung, L. W.;
Morokuma, K.; Nozaki, K. J. Am. Chem. Soc. 2009, 131, 14088.
6) Wucher, P.; Goldbach, V.; Mecking, S. Organometallics 2013, 32,
(
4
516.
(7) Wucher, P.; Caporaso, L.; Roesle, P.; Ragone, F.; Cavallo, L.;
Mecking, S.; Go
108, 8955.
8) For cyclopolymerizations of nonfunctionalized dienes cf.:
a) Coates, G. W.; Waymouth, R. M. J. Am. Chem. Soc. 1991, 113,
270. (b) Shi, X.; Wang, Y.; Liu, J.; Cui, D.; Men, Y.; Li, Y.
̈
ttker-Schnetmann, I. Proc. Natl. Acad. Sci. U.S.A. 2011,
(
(
6
Macromolecules 2011, 44, 1062. (c) Crawford, K. E.; Sita, L. R. J. Am.
Chem. Soc. 2013, 135, 8778. For reaction of ethylene with
functionalized 1,6-dienes catalyzed by α-diimine Pd catalysts cf.:
ASSOCIATED CONTENT
Supporting Information
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*
S
II
(d) Okada, T.; Park, S.; Takeuchi, D.; Osakada, K. Angew. Chem., Int.
Ed. 2007, 46, 6141. (e) Park, S.; Takeuchi, D.; Osakada, K. J. Am.
Chem. Soc. 2006, 128, 3510.
(9) Copolymerization of ethylene with allyl acrylate by 1-pyridine
AUTHOR INFORMATION
Notes
was shown to afford cyclic units (mixtures of five- and six-membered
cycles) along with a similar amount of repeat units with a remaining
intact double bond: Daigle, J.-C.; Piche, L.; Arnold, A.; Claverie, J. P.
ACS Macro Lett. 2012, 1, 343. Note that allyl moieties generally
incorporate less readily vs acrylates. Consequently, no clear effect on
molecular weights was observed.
The authors declare no competing financial interest.
(10) Daigle, J.-C.; Piche, L.; Claverie, J. P. Macromolecules 2011, 44,
ACKNOWLEDGMENTS
1760.
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(11) Note that, due to the extreme slow rate of insertion of AA into
Z.J. is grateful to the Alexander von Humboldt Foundation for
a postdoctoral research fellowship and to the University of
Konstanz for the EU FP7 Marie Curie Zukunftskolleg
Incoming Fellowship Programme (grant no. 291784). Inigo
lutidine-coordinated complex 3 at 25 °C, the alternative 3-LiCl/AgBF4
catalyst system was used for the kinetic insertion study. See ref 7.
̈
Gottker-Schnetmann, Philipp Wucher, and Philipp Roesle are
gratefully acknowledged for helpful discussions. The authors
also thank Lars Bolk for GPC experiments.
D
J. Am. Chem. Soc. XXXX, XXX, XXX−XXX