Are Metallocene-Acetylene (M = Ti, Zr, Hf) Complexes Aromatic Metallacyclopropenes?

Jemmis, Eluvathingal D and Roy, Subhendu and Burlakov, VV and Jiao, H and Klahn, M and Hansen, S and Rosenthal, U (2010) Are Metallocene-Acetylene (M = Ti, Zr, Hf) Complexes Aromatic Metallacyclopropenes? In: Organometallics, 29 (1). pp. 76-81.

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Abstract

The bonding nature of metallocene acetylene complexes Cp2M(eta(2)-H3SiC2SiH3) 1M and CP2M (eta(2)- HC2H) 1M' (M = Ti, Zr, Hf) wits studied by density functional theory method. It is found that this acetylene complex has indeed it metallacyclopropene moiety with two in-plane M-C sigma-bonds and one out-of-plane pi-bond interacting with the metal center, resulting in the formation of it delocalized three-center and two-electron (3c-2e) system. Along with its delocalized out-of-plane bonding, this complex has been characterized its aromatic on the basis of the computed stabilizing energy and negative nucleus-independent chemical shifts (NICS). The aromatic stabilization increases from Ti to Zr and Hf, and this is because of the increased charge separation between the CP2M fragment and the H3SiC2SiH3 (also HC2H) unit. The decrease of the M-C bond length from Zr to Hf is ttributed to the increased s character of both M and C hybridization of the M-C a-bonds.

Item Type:	Journal Article
Publication:	Organometallics
Publisher:	American Chemical Society
Additional Information:	Copyright for this article belongs to American Chemical Society.
Department/Centre:	Division of Chemical Sciences > Inorganic & Physical Chemistry
Date Deposited:	27 Jan 2010 09:55
Last Modified:	19 Sep 2010 05:54
URI:	http://eprints.iisc.ac.in/id/eprint/25454

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