Oxidation,Redox Disproportionation and Chain Termination Reactions Catalysed by the Pd‐561 Giant Cluster

Redox disproportionation of benzyl alcohol to benzaldehyde and toluene catalysed by the Pd₅₆₁phen₆₀(OAc)₁₈₀ (phen=1,10‐phenanthroline) giant cluster 1 under anaerobic conditions was found, whereas in an O₂ atmosphere cluster 1 catalyses the oxidation of benzyl alcohol to benzaldehyde and inhibits further oxidation of the latter. A study of the AIBN‐initiated and non‐initiated oxidation of benzyl alcohol, sec‐butyl alcohol and styrene in the presence of cluster 1 revealed that cluster 1 performs three functions in the oxidation reactions: 1) catalysis of polar oxidation of the substrates with O₂, 2) termination of the chains of radical oxidation, and 3) catalysis of redox disproportionation.