Reduction-Oxidation Properties of Organotransition-metal Complexes. Part 23. Pentaphenylcyclopentadienyl Carbonyl Complexes of Cobalt and Rhodiu

DOI: 10.1039/DT9860001613

Source and publish data:

Journal of the Chemical Society, Dalton Transactions p. 1613 - 1618 (1986)

Update date:2022-07-29

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Authors:

Conelly, Neil G.

Raven, Stephen J.

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Article abstract of DOI:10.1039/DT9860001613

The reaction of or <2> with C5Ph5Br and zinc dust in tetrahydrofuran (thf) gives (1,M=Co or Rh); in the case of rhodium, the intermediate is isolable if the reaction is carried out in benzene.In the presence of ⁺, (1,M=Rh) undergoes oxidatively-induced carbonyl substitution with ligands, L; for L=P(OPh)3, the formation of <2,M=Rh, L=P(OPh)3> is catalytic in the oxidant.The complexes (2) are also prepared via (a) the substitution of with PPh3 or AsPh3 and subsequent reduction by , (b) reduction of (3,M=Co) in the presence of P(OMe)3 or P(OPh)3, or (c) reduction of (η-C5Ph5)> (5) in the presence of CO.Complexes (3,M=Co or Rh) are prepared from (1) and iodine in toluene-hexane at 0 deg C; the rhodium complex (3,M=Rh) is reduced by to give <2>.Compound (5) results from the addition of P(OMe)3 to <2> (4), which is the product of the reaction between (1,M=Rh) and bromine in CH2Cl2.The compounds (2) undergo two one-electron oxidations at a platinium electrode in CH2Cl2; the first is reversible and the second is irreversible.The monocations <2(+),M=Rh,L=PPh3, P(OPh)3, or AsPh3> have been characterised in solution by i.r. and e.s.r. spectroscopy.Low-temperature e.s.r. spectroscopy has shown that the radical cation ⁺ is stable at -196 deg C.

Full text of DOI:10.1039/DT9860001613

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