Successive alkylation of Pt II by RI to form bis-organoplatinum(IV) derivatives as key steps for cross-electrophile coupling

Abstract A solvent-specific reduction of Pt IV iodo complexes into Pt II by iodide ions was found: in acetone, Pt IV iodo complexes are almost quantitatively reduced into Pt II , and iodine, which is formed upon the reduction, is bound in a poorly soluble polymeric complex with NaI and acetone. The revealed solvent-specific reduction of Pt IV into Pt II was used for sequential alkylation of Pt II iodo complexes with iodoacetone to form mono-, bis-, and tris-acetonyl Pt IV derivatives and also with iodoacetic acid to give mono- and bis-carboxymethyl Pt IV complexes. The reaction of iodoacetic acid is accompanied by its catalytic reduction into acetic acid. The organic ligands in the formed organoplatinum compounds are mutually cis , which is essential for further accomplishment of C-C coupling reactions.