Unstable intermediates. Part CLIII. Electron spin resonance spectra and structure of dichlorophosphoranyl radicals
- 1 January 1975
- journal article
- research article
- Published by Royal Society of Chemistry (RSC) in J. Chem. Soc., Dalton Trans.
- No. 12,p. 1164-1167
- https://doi.org/10.1039/dt9750001164
Abstract
A range of dichlorophosphoranyl radicals [(RO)P(O)Cl2][graphic omitted] have been prepared by exposure of the neutral molecules, (RO)P(O)Cl2, to 60Co γ-rays at 77 K [R = Me, Et, Ph, C10H7(α-naphthyl), MeOCH2CH2, or ClCH2CH2]. Well resolved e.s.r. spectra obtained from [(MeO)POCl2][graphic omitted] and [(EtO)POCl2][graphic omitted] have enabled the components of the 31P and 35,37Cl hyperfine-coupling tensors to be derived. The results show that both tensors are nearly axial, but their principal axes are at right angles to each other. The two chlorine ligands must be nearly coaxial with the phosphorus atom and they share ca. 50% of the total spin density, the remainder being confined to 3s and 3p orbitals on phosphorus.Keywords
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