Heterolytic OO Bond Cleavage of Copper(I)‐Alkylperoxide Complex Generating a Putative Copper(II)‐Oxyl Intermediate

Reactivity of a copper(I) complex supported by TMG 3 tren (L: (1,1,1‐tris(2‐( N 2 ‐(1,1,3,3‐tetramethylguanidino))ethyl)amine) toward cumene hydroperoxide (CmOOH) was examined to search possible formation of a copper(II)‐oxyl ((L)Cu II –O•) species via OO bond heterolysis of a copper(I) cumyl peroxide adduct intermediate. The major product was copper(II) hydroxide complex ((L)Cu II –OH), which could be formed from (L)Cu II –O• intermediate via hydrogen atom abstraction (HAA) from cumyl alcohol (CmOH, one of the products in the OO bond heterolysis process) or a solvent molecule (propionitrile). The (L)Cu II –O• intermediate also induced HAA from one of the methyl groups of TMG substituents to give a ligand‐hydroxylated complex. The reaction mechanism was discussed based on the product analyses and DFT calculations.