Electron paramagnetic resonance spectra of rhenium tetrachloride oxide and some of its adducts
- 1 January 1975
- journal article
- research article
- Published by Royal Society of Chemistry (RSC) in J. Chem. Soc., Dalton Trans.
- No. 1,p. 50-55
- https://doi.org/10.1039/dt9750000050
Abstract
X-Band e.p.r. spectra of Re(O)Cl4, [Re(O)Cl4(NCMe)], [Re(O)Cl4(OPCl3)], and [Ph4As][Re(O)Cl5] have been recorded at 77 K and are analysed in detail. The metal-ion spin–orbit coupling constant and the parameter P= 2·002gReβeβN〈ψ|r–3|ψ〉 have been estimated to be ca. 2 400 and 0·033 cm–1 respectively. Spin-Hamiltonian parameters are listed for each substance and are equated to the atomic-orbital coefficients in some of the molecular orbitals involved in bonding in these molecules. The unpaired electron lies in the metal-ion 5dxy orbital and is strongly delocalised (33%) on to the chloride ligands. g∥ Is greater than g⊥ and this is shown to be essentially due to charge-transfer mixing through spin–orbit coupling at the chlorine atoms. Changes in the spin-Hamiltonian parameters when a sixth ligand is added to Re(O)Cl4 are accounted for. Hückel LCAO molecular-orbital calculations on Re(O)Cl4 appear to give a reasonable description of its ground state.Keywords
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