Photo-oxidation of alcohols by hexachlorometalate(IV) ions (M = Pt, Pd, or Ir): spin trapping and matrix isolation electron spin resonance studies

Abstract

Spin-trapping studies reveal that whereas the mild (λ > 380 nm) photolysis of ions [MCl₆]^2–(M = Pd, Pt, or Ir) in alcohol (RCH₂OH)-water mixtures leads invariably to RĊHOH, in pure alcoholic media many of the oxidations lead to RCH₂[graphic omitted]. Prolonged, wide-band photolysis leads to the production of H atoms. At 77 K, wide-band photolysis leads to the production of platinum(III) and palladium(III) centres, identified by their g_⊥ features, in addition to the expected C-centred organic radicals.