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(a) Certain Ni(II) catalysts convert R-olefins to oligomers with degrees of polymerization of ca. 4-20: (a) Möhring, V. M.; Fink, G. Angew. Chem., Int. Ed. Engl. 1985, 24, 1001-1003.
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(a) 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.
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A palladium-catalyzed reaction of ethylene with methyl acrylate has been reported to give low molecular weight materials (Mn ≤ 4100), but no detailed product characterizations were given: Drent, E.; Pello, D. H. L.; Jager, W. W. Eur. Pat. Appl. 1994, 589527.
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(a) The use of α-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.
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2642648247
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Elsevier. For the development and synthesis of the N-aryl-substituted R-diimine ligands used in this research
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(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:
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(c) R = H, Me: tom Dieck, H.; Svoboda, M.; Grieser, T. Z. Naturforsch 1981, 36b, 823-832.
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39
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0002574018
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Elsevier: C. J.; Smeets, W. J. J.; Spek, A. L.; Benedix, R.
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(a) 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.
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80355127755
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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M. S.; Arthur, S. D.; Feldman, J.; Johnson, L. K.; McLain, S. J.; McCord, E. F.; Mecking, S.; Wang, L.; Wang, Y., unpublished results
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(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.
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41
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80355123489
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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 lowtemperature 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
-
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 lowtemperature 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.
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42
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80355130579
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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
-
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.
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43
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80355130577
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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
-
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.
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44
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0025992964
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(a) 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 (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.
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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 tertbutylacrylate (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 phenanthroline complexes, cf.: Rix, F. C.; Brookhart, M.; White, P. S. J. Am. Chem. Soc. 1996, 118, 4746-4764.
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