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Donor-Ligand-Substituted Cyclopentadienylchromium(III) Complexes:  A New Class of Alkene Polymerization Catalyst. 2. Phosphinoalkyl-Substituted Systems

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Döhring,  Arno
Research Department Jolly, Max-Planck-Institut für Kohlenforschung, Max Planck Society;

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Jensen,  Vidar R.
Research Department Thiel, Max-Planck-Institut für Kohlenforschung, Max Planck Society;

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Jolly,  Peter W.
Research Department Jolly, Max-Planck-Institut für Kohlenforschung, Max Planck Society;

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Thiel,  Walter
Research Department Thiel, Max-Planck-Institut für Kohlenforschung, Max Planck Society;

Weber,  Jan C.
Research Department Jolly, Max-Planck-Institut für Kohlenforschung, Max Planck Society;

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om010146m_s.pdf
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Citation

Döhring, A., Jensen, V. R., Jolly, P. W., Thiel, W., & Weber, J. C. (2001). Donor-Ligand-Substituted Cyclopentadienylchromium(III) Complexes:  A New Class of Alkene Polymerization Catalyst. 2. Phosphinoalkyl-Substituted Systems. Organometallics, 20(11), 2234-2245. doi:10.1021/om010146m.


Cite as: https://hdl.handle.net/11858/00-001M-0000-0024-20DA-A
Abstract
A series of phosphinoalkyl-substituted cyclopentadienylchromium complexes, e.g., (η15-R2PC2H4C5H4)CrCl2, have been synthesized. The complexation of the P atom to the chromium has been confirmed by crystal structure determinations. Activated by methylalumoxane (MAO), these compounds catalyze the oligomerization and polymerization of ethylene. The catalytic activity and the degree of oligomerization are controlled by the steric properties of the substituents on the donor atom:  the smaller the substituent, the greater the activity and the lower the molecular weight of the oligomer. Density functional calculations indicate that propagation and termination through β-hydrogen transfer are competitive for small substituents and that the latter process, which involves spin inversion, becomes selectively disfavored with increasing size of the substituents. For large substituents β-hydrogen elimination to the chromium atom is found to be the preferred route for termination, although this reaction is less facile than insertion.