Abstract
On photolysis cis-[MH 2(DMPE) 2] (M = Fe, Ru; Os; DMPE = Me 2PCH 2CH 2PMe 2) and cis-[MH 2(DPPE) 2] (M = Fe, Ru, Os; DPPE = Ph 2PCH 2CH 2PPh 2) readily lose H 2 by concerted coupling of the two hydrogen atoms. The photoreactions generate the extremely reactive intermediates [M(DMPE) 2] and [M(DPPE) 2] which react with tetracyanoethylene (TCNE) to form metal(II) complexes: [C 2(CN) 3M(DMPE) 2CN], [C 2(CN) 3M(DPPE) 2CN] via free-radical oxidative addition processes. The reactive species may be trapped to give zerovalent compounds upon irradiation of the title compounds in the presence of Lewis ligand L (e.g. [LM(DMPE) 2], [LM(DPPE) 2];L = CO, C 2H 4).
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