Electronic Structure of the Alkyne-Bridged Dicobalt Hexacarbonyl Complex Co2 μ-C2H2 (CO)6: Evidence for Singlet Diradical Character and Implications for Metal−Metal Bonding

Platts, James Alexis ORCID: https://orcid.org/0000-0002-1008-6595, Evans, Gareth James S., Coogan, Michael Peter and Overgaard, Jacob 2007. Electronic Structure of the Alkyne-Bridged Dicobalt Hexacarbonyl Complex Co2 μ-C2H2 (CO)6: Evidence for Singlet Diradical Character and Implications for Metal−Metal Bonding. Inorganic Chemistry 46 (16) , pp. 6291-6298. 10.1021/ic070278t

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Abstract

A series of ab initio calculations are presented on the alkyne-bridged dicobalt hexacarbonyl cluster Co2 μ-C2H2 (CO)6, indicating that this compound has substantial multireference character, which we interpret as evidence of singlet diradical behavior. As a result, standard theoretical methods such as restricted Hartree−Fock (RHF) or Kohn−Sham (RKS) density functional theory cannot properly describe this compound. We have therefore used complete active space (CAS) methods to explore the bonding in and spectroscopic properties of Co2 μ-C2H2 (CO)6. CAS methods identify significant population of a Co−Co antibonding orbital, along with Co−π* back-bonding, and a relatively large singlet−triplet energy splitting. Analysis of the electron density and related quantities, such as energy densities and atomic overlaps, indicates a small but significant amount of covalent bonding between cobalt centers.

Item Type:	Article
Date Type:	Publication
Status:	Published
Schools:	Chemistry
Subjects:	Q Science > QD Chemistry
Publisher:	American Chemical Society
ISSN:	0020-1669
Last Modified:	18 Oct 2022 13:21
URI:	https://orca.cardiff.ac.uk/id/eprint/13581

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