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Hydrogen Abstraction and Dimerisation Reactions of Some Organo-transition Metal Free Radicals by Judith A. Armstead; David J. Cox; Reg Davis is a Chemistry article available to read on EtoBox.

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The 17electron species [M(CO),,L,] (M = Mn, Re, x = 0; M = Mn, Re; L = PhsP, x = 1,2; M = Mn, Re; L = (o-MeC6H40)3P, x = 2; M = Mn; L = @CGH,O),P, (PhO)J', x = 2; M = Mn; L = P(OMe)s, x = 3) have been generated by one electron oxidation of the corresponding anions and show typical radical reactivity, undergoing dimerisation or hydride abstraction in reactions controlled by steric effects. Evidence is presented for the source of the hydrogen atom. The 19electron species [M(CO),(q7-C,H,)]-(M = Cr, MO) and [Fe(CO),($-&II,)] -, generated by reduction of the corresponding cations, undergo dimerisation at the organic ligand. Similar treatment of [Fe(CO),-L(q-cp)]+ (L = CO, PPh,, P(OPh),, Me&O) yields [Fe,(CO),(q-cp),] and these reduction reactions are rationahsed in terms of the nature of the HOMO in the intermediate radical. Similar reduction of [Rh(diphos),] \* yield the 17eIectron intermediate [Rh(diphos),] and this also undergoes hydrogen abstraction.

Who reads Hydrogen Abstraction and Dimerisation Reactions of Some Organo-transition Metal Free Radicals?

Author

Judith A. Armstead; David J. Cox; Reg Davis

Publisher

Elsevier Science; Elsevier ; Elsevier BV (ISSN 0022-328X)

Published

1982

Language

EN

Field

Chemistry (Physical Sciences)