Radiation induced reactions of some platinum metal nitrosyl complexes containing tertiary phosphine, arsine and stibine ligands

Abstract

Photochemical reactions of complexes of the stoichiometric type M(NO)X 3(Ph 3Y) 2 for MRu, Os; YP, As, Sb; XCl, Br, I and M(NO)X 2(Ph 3Y)2 for MRh, Ir; YP, As; XCl, Br, I, have been investigated. In many of the reactions one of the organo-pnictide ligands (Ph 3Y) is oxidized and remains coordinated (through the oxygen) to the transition metal. In the case of rhodium and iridium complexes, however, different reactions occur with complete loss of NO from the metal centre. Oxidation studies of the free ligands, and mass spectrometric analysis of gaseous reaction products have been used to elucidate the nature of the oxidizing agent for the complexes. The photochemical reactions of the complexes Ru(NO)X 3(Et 2PhP) 2 for XCr, Br, I have also been studied and they differ from the others in that isomerization occurs from the trans isomer to the cis-meridional isomer.