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One-electron Reduction of Di-imidosulphur Compounds, S(NR)2, and some Complexes of Group 6A Metal Carbonyl Derivatives containing S(NR)2 Ligands: Studies of the Radical Products by Electron Spin Resonance Spectroscopy

DOI: 10.1039/DT9800000880

Source and publish data:

Journal of the Chemical Society, Dalton Transactions p. 880 - 887 (1980)

Update date:2022-08-04

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Authors:

Hunter, John A.Hunter, John A.

King, BoydKing, Boyd

Lindsell, W. EdwardLindsell, W. Edward

Neish, Margaret A.Neish, Margaret A.

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Article abstract of DOI:10.1039/DT9800000880

Reduction of the di-imidosulphur compounds, S(NR)2 (R=But, Ph, 4-MeC6H4, or 4-O2NC6H4), in 1,2-dimethoxyethane solution with a potassium mirror in vacuo gives fairly stable solutions of the corresponding anion radicals - which have been studied by e.s.r. spectroscopy.The frozen-solution e.s.r. spectrum of Kt)2> has also been recorded.Isotropic coupling constants A(14N), A(1H) and, for R=But, A(33S) have been deduced and analysed in terms of the electronic structures of the radicals using empirical electron-density relationships.Some CNDO/2 and INDO calculations have been made and the experimental and calculated electron-spin densities compared.Variable-temperature e.s.r. measurements have given no indication of the presence of distinct geometric isomers of the anions in solutions.The model calculations suggest that the E/E conformation is most stable and that interconversion to give the E/Z or Z/Z forms is unlikely.The experimental evidence in all cases indicates the two nitrogen atoms to be magnetically equivalent.Alkali-metal isotropic coupling constants A(MI) for the species MIt)2> (MI=7Li, 23Na, or 39K) have been estimated and indicate that the metal-anion interaction increases in the order K < Na < Li.Potassium-metal reduction of t)2)> (M=Cr, Mo, or W) produces the corresponding anions with well defined isotropic e.s.r. spectra.Values for A(14N) and A(M) (M=95/97Mo or 183W) have been deduced and the spectra analysed.The results suggest that the unpaired electron is located mainly in the S(NBut)2 ligand.CNDO/2 calculations for the chromium anion are consistent with this observation.Attempts to produce - have been unsuccesful except for M=Cr, when an unstable species is formed.A tentative analysis of the e.s.r. spectrum of this radical anion is presented.

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