Preparation and properties of mer-[ReCl(N2)(CNR){P(OMe)3}3](R = Me, Et, But, C6H4Me-4, or C6H4Cl-4) and [ReCl(N2)(CNMe)(PPh3){P(OEt)3}2]. X-Ray crystal structure of mer-[ReCl(N2)(CNMe){P(OMe)3}3] and reductive cleavage of the lsocyanide ligands to primary amines upon protonation

Abstract

The complexes [ReCl(N₂)(CNR){P(OMe)₃}₃](R = Me, Et, Bu^t, C₆H₄Me-4, or C₆H₄Cl;-4) and [ReCl(N₂)(CNMe)(PPh₃){P(OEt)₃}₂] have been prepared by reaction of the corresponding diazenido-species [ReCl₂(NNCOPh)(PPh₃)_x{P(OR′)₃}_3–x](x= 0 or 1; R′= Me or Et) with the appropriate isocyanide in refluxing methanol, and the X-ray crystal structure of mer-[ReCl(N₂)(CNMe){P(OMe)₃}₃] is reported. In these complexes the isocyanide ligand undergoes protic attack with cleavage of the unsaturated NC bond to afford the corresponding primary ammonium salt.