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The crucial importance of agostic interactions in intermediates formed in propylene polymerization using neutral salicyladiminato palladium(II) and nickel complexes as catalysts

Liu, Y. and Drew, M.G.B. (2007) The crucial importance of agostic interactions in intermediates formed in propylene polymerization using neutral salicyladiminato palladium(II) and nickel complexes as catalysts. Journal of Molecular Structure-Theochem, 821 (1-3). pp. 30-41. ISSN 0166-1280

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To link to this item DOI: 10.1016/j.theochem.2007.06.017

Abstract/Summary

The structures of intermediates formed in propylene polymerisation using neutral salicyladiminato palladium(II) and nickel(II) complexes as catalysts have been investigated using density functional theory. Calculations show that all low energy intermediates contain agostic interactions either between the metal and a hydrogen from the added propylene forming four- or five-membered chelate rings, or, when a phenyl ring is present, between the metal and an aromatic C-C bond. The agostic interactions with the metal are concomitant with changes in ligand dimensions and electronic properties. In particular when a metal to hydrogen bond is formed, there is a lengthening of the C-H bond. Significant differences are found for the agostic interactions with palladium and nickel in that for Pd there is a clear preference for specific intermediates but for Ni there are several different structures with similar energies which are likely to lead to a greater variety of products on further polymerisation. (c) 2007 Elsevier B.V. All rights reserved.

Item Type:Article
Refereed:Yes
Divisions:Faculty of Life Sciences > School of Chemistry, Food and Pharmacy > Department of Chemistry
ID Code:11435
Uncontrolled Keywords:Heck reaction, density functional theory, agostic interactions, salicyladiminato ligands, palladium, nickel, HECK REACTION, C-H, HYDROGEN, LIGAND, BONDS, STABILITY, MECHANISM, OLEFINS, METALS

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