Reduction-Oxidation Properties of Organotransition-metal Complexes. Part 8. Formation and Reactivity of the Radical Cations (1+), and the Mechanism of the Oxidative Elimination Reaction of with Halogens

DOI: 10.1039/DT9800000579

Source and publish data:

Journal of the Chemical Society, Dalton Transactions p. 579 - 585 (1980)

Update date:2022-08-03

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Authors:

Baker, Paul K.

Connelly, Neil G.

Jones, Brian M. R.

Maher, John P.

Somers, Karen R.

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Article abstract of DOI:10.1039/DT9800000579

Cyclic-voltammetric studies in CH2Cl2 show that <1; L=PPh3, AsPh3, PMePh2, P(NMe2)3, or P(OPh)3; L₂=Ph2PCH2CH2PPh2 (dppe) or Ph2PCH2PPh2 (dppm)> undergoes one-electron oxidation to the radical cation (1+) (2) which may be chemically generated from (1) using silver(I) salts or .The complex (2; L=PPh3) reacts with halogens to give diamagnetic (3) which yields 4-n(PPh3)_n> (4; X=I, n=1; X=Br, n=1 and 2; X=Cl, n=2) with X(1-).Halide ions react directly with (2; L=PPh3) to give mixtures of (1; L=PPh3) and (4) via the paramagnetic intermediate (5).A mechanism is proposed for the oxidative elimination reaction of (1) with halogens; the reactions of (2), and i.r. stopped-flow kinetic studies, implicate (2) and (5) as redox-active intermediates.

Full text of DOI:10.1039/DT9800000579

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