Oxidatively induced reductive coupling of PPh2 and Ph groups mediated by a platinum cluster: synthesis and crystal structure of the butterfly cluster [Pt3(µ3-AgO2CCF3)(µ-PPh2)3Ph(PPh3)2]·C6H6

Abstract

Recombination of a PPh₂ bridge and a terminal Ph group, originally produced by P–C bond breaking of PPh₃ in a Pt complex, is achieved by the two-electron oxidation of the cluster [Pt₃(µ-PPh₂)₃Ph(PPh₃)₂] 1 with I₂, followed by reductive coupling of both fragments, thus restoring a PPh₃ ligand in the cationic cluster [Pt₃(µ-I)(µ-PPh₂)₂(PPh₃)₃]I 2; the electron-rich character of 1 is evidenced by its reaction with AgO₂CCF₃ which leads to the formation of the structurally characterized [Pt₃(µ₃-AgO₂CCF₃)(µ-PPh₂)₃-Ph(PPh₃)₂] 3.