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Theoretical Studies on the Structure and Bonding of Metallacyclocumulenes, -cyclopentynes, and -cycloallenes

Roy, Subhendu and Jemmis, Eluvathingal D and Ruhmann, Martin and Schuz, Axel and Kaleta, Katharina and Beweries, Torsten and Rosenthal, Uwe (2011) Theoretical Studies on the Structure and Bonding of Metallacyclocumulenes, -cyclopentynes, and -cycloallenes. In: Organometallics, 30 (10). pp. 2670-2679.

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Official URL: http://pubs.acs.org/doi/abs/10.1021/om2000037

Abstract

In this paper, we compare the electronic structure of the hafnacycloallene complex Cp(2)HfC(4)Rr'(2)R `' (5Hf), which was previously described by Erker et al., with those of the titanium, zirconium, and hafnium complexes Cp(2)M(eta(4)-RHC(4)HR) (3M; i.e. metallacyclopent-2,3,4-trienes, metallacyclocumulenes) and Cp(2)M(eta(2)-R(2)C(4)R(2)) (4M; i.e. 1-metallacyclopent-3-ynes) using density functional theory (BP86/LANL2DZ) calculations. Moreover, the eta(3)-phenylallenyl zirconocene complex 7Zr, which was synthesized by Wojcicki et al., is included for the comparison. These calculations and extended Huckel calculations show that the bonding in complex 5Hf is remarkably similar to that of complexes 4M and 7Zr. An analysis of the structural parameters and bonding reveals that the unique interaction of the internal carbon atoms along with the terminal carbon atoms with the bent-metallocene moiety is the reason for the unusual stability of these metallacycles. The molecular orbital analysis further suggests that complex 5Hf can react with another metal fragment to give the bimetallic complexes 9 and 10. The electronic structures of complexes 3M, 4M, 5Hf, and 7Zr have been comparatively studied to get a general understanding of the bonding in these metallacycles.

Item Type: Journal Article
Additional Information: Copyright of this article belongs to American Chemical society.
Department/Centre: Division of Chemical Sciences > Inorganic & Physical Chemistry
Depositing User: Id for Latest eprints
Date Deposited: 16 Sep 2011 07:00
Last Modified: 16 Sep 2011 07:00
URI: http://eprints.iisc.ac.in/id/eprint/40045

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