en
Scientific article
Open access
English

EPR and DFT Studies of the Structure of Phosphinyl Radicals Complexed by a Pentacarbonyl Transition Metal

Published inThe journal of physical chemistry. A, vol. 110, no. 31, p. 9736-9742
Publication date2006
Abstract

Paramagnetic complexes M(CO)5P(C6H5)2, with M = Cr, Mo, W, have been trapped in irradiated crystals of M(CO)5P(C6H5)3 (M = Cr, Mo, W) and M(CO)5PH(C6H5)2 (M = Cr, W) and studied by EPR. The radiolytic scission of a P−C or a P−H bond, responsible for the formation of M(CO)5P(C6H5)2, is consistent with both the number of EPR sites and the crystal structures. The g and 31P hyperfine tensors measured for M(CO)5P(C6H5)2 present some of the characteristics expected for the diphenylphosphinyl radical. However, compared to Ph2P•, the 31P isotropic coupling is larger, the dipolar coupling is smaller, and for Mo and W compounds, the g-anisotropy is more pronounced. These properties are well predicted by DFT calculations. In the optimized structures of M(CO)5P(C6H5)2 (M = Cr, Mo, W), the unpaired electron is mainly confined in a phosphorus p-orbital, which conjugates with the metal dxz orbital. The trapped species can be described as a transition metal-coordinated phosphinyl radical.

Research group
Citation (ISO format)
NDIAYE, Bassirou et al. EPR and DFT Studies of the Structure of Phosphinyl Radicals Complexed by a Pentacarbonyl Transition Metal. In: The journal of physical chemistry. A, 2006, vol. 110, n° 31, p. 9736–9742. doi: 10.1021/jp061960w
Main files (1)
Article (Published version)
accessLevelPublic
Identifiers
ISSN of the journal1089-5639
641views
667downloads

Technical informations

Creation09/21/2009 4:22:55 PM
First validation09/21/2009 4:22:55 PM
Update time03/14/2023 3:14:17 PM
Status update03/14/2023 3:14:17 PM
Last indexation01/15/2024 6:58:10 PM
All rights reserved by Archive ouverte UNIGE and the University of GenevaunigeBlack