Hydrogen abstraction and dimerisation reactions of some organo-transition metal free radicals |
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| Authors: | Judith A Armstead David J Cox Reg Davis |
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| Institution: | School of Chemical and Physical Sciences, Kingston Polytechnic, Penrhyn Road, Kingston-upon-Thames, KT1 2EE Great Britain |
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| Abstract: | The 17-electron species M(CO)5χLχ] (M Mn, Re, χ 0; M Mn, Re; L Ph3P, χ 1, 2; M Mn, Re; L (o-MeC6H4O)3P, χ 2; M Mn; L (p-ClC6H4O)3P, (PhO)3P, χ 2; M Mn; L P(OMe)3, χ 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 19-electron species M(CO)3(η7-C7H7)]? (M Cr, Mo) and Fe(CO)3(η5-C6H7)]?, generated by reduction of the corresponding cations, undergo dimerisation at the organic ligand. Similar treatment of Fe(CO)2-L(η-cp)]+ (L CO, PPh3, P(OPh)3, Me2CO) yields Fe2(CO)4(η-cp)2] and these reduction reactions are rationalised in terms of the nature of the HOMO in the intermediate radical. Similar reduction of Rh(diphos)2]+ yield the 17-electron intermediate Rh(diphos)2] and this also undergoes hydrogen abstraction. |
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| Keywords: | Author to whom correspondence should be addressed |
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