Electronic structure of ruthenium(II) polyynyl complexes

Koentjoro, O.F.; Rousseau, R.; Low, P.J.

Abstract

The electronic structure of the polyynyl complexes [Ru{(C equivalent toC)nR}(PH3)(2)CP] (n = 1-6; R = H, CH3, C6H5, C6H4NH2-P, C6H4NO2-P, CN), the diynyl compounds [Ru{(C equivalent toC)(2)R}CO)(2)CP], and the oxidized species [Ru{(C equivalent toC),C6H5}(PH3)(2)CP](+) have been studied using DFT methods. The optimized geometries are in good agreement with the few experimental structures available. The electronic structures are best described in terms of a strong sigma - bonding component and a weaker interaction between the filled metal d orbitals and filled polyyne pi orbitals. The charge distribution in the molecules and the energies and localization of the frontier orbitals have been examined to help rationalize the reactivity patterns emerging for this important class of compounds.

Citation

Koentjoro, O., Rousseau, R., & Low, P. (2001). Electronic structure of ruthenium(II) polyynyl complexes. Organometallics, 20(22), 4502-4509. https://doi.org/10.1021/om010304%2B

• Journal Article Type: Article
• Publication Date: 2001-10
• Deposit Date: Apr 19, 2007
• Journal: Organometallics
• Print ISSN: 0276-7333
• Electronic ISSN: 1520-6041
• Publisher: American Chemical Society
• Peer Reviewed: Peer Reviewed
• Volume: 20
• Issue: 22
• Pages: 4502-4509
• DOI: https://doi.org/10.1021/om010304%2B
• Public URL: https://durham-repository.worktribe.com/output/1557029