Low-temperature spectroscopic observation of chain growth and migratory insertion barriers in (α-diimine)Ni(II) olefin polymerization catalysts [5]

Journal of the American Chemical Society

Volumn 121, Issue 45, 1999, Pages 10634-10635

  Svejda, Steven A ^a   Johnson, Lynda K ^a   Brookhart, Maurice ^a  

^a University of North Carolina at Chapel Hill   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

ALKENE; IMINE; NICKEL;

CATALYSIS; CATALYST; CHEMICAL STRUCTURE; COMPLEX FORMATION; CONCENTRATION RESPONSE; KINETICS; LETTER; NUCLEAR MAGNETIC RESONANCE SPECTROSCOPY; POLYMERIZATION; PROTON TRANSPORT; SPECTROSCOPY; TEMPERATURE DEPENDENCE;

EID: 0033579145     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja991931h     Document Type: Letter

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29. 2 eliminate ethane readily above 0 °C.
30. The nickel dimethyl complexes were prepared using a procedure similar to that earlier reported: Svoboda, M.; tom Dieck, H. J. Organomet. Chem. 1980, 191, 321-328. See Supporting Information for experimental details.
31. +: n = 2 (first insertion product), n = 4 (second insertion), and n = 6 (third insertion). See Supporting Information for illustrated spectra.
32. Water adduct 4a was used instead of ether adduct 3a because ether displacement by propylene is competitive with migratory insertion, whereas formation of methyl propylene complex 8a from 4a is rapid at -80 °C.
33. A β-agostic resting state in polymerization of cyclopentene using Ni and Pd diimine complexes has been reported: McLain, S. J.; Feldman, J.; McCord, E. F.; Gardner, K. H.; Teasley, M. F.; Coughlin, E. B.; Sweetman, K. J.; Johnson, L. K.; Brookhart, M. Macromolecules 1998, 31, 6705-6707.
34. Species 9a is highly dynamic and exhibits broad agostic signals even at -120 °C at -12.3, -12.5, and -13.2 ppm in a ∼2:6:2 ratio. From bulk polymer analyses, both 1,2 and 2,1 modes of insertion are observed; thus 9a may exist as a dynamic, interconverting mixture of as many as five agostic nickel-butyl complexes. Structural assignments are not possible at this stage. Only one isomer is shown in Scheme 4 for simplicity.
35. 2F vs toluene) and had different counterions.
36. Gates, D. P.; Svejda, S. A.; Brookhart, M. Unpublished results.
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