Complexes of the platinum metals. Part 41. Oxidative-substitution reactions at ruthenium(II) and osmium(II) involving N,N′-diphenylamidinate ligands

Abstract

Ruthenium(II) and osmium(II) complexes [MCl₂(PPh₃)₃] undergo oxidative-substitution reactions with N,N′-diphenylamidines PhNC(R)–NHPh (R = H, Me, Et or Ph) under mild conditions to form the ruthenium(III) and osmium(III) products [MCl₂{PhNC(R)NPh}(PPh₃)₂](M = Ru; R = H or Ph; M = Os, R = H, Me or Ph). However, in contrast to other systems of this type, more prolonged reaction times lead to further substitution and/or oxidation steps which afford the ruthenium(III) complexes [RuCl{PhNC(R)NPh}₂(PPh₃)] and the osmium(IV) species [OsCl₂{PhNC(R)NPh}₂](R = Me, Et or Ph). The crystal structure of trans-[OsCl₂{PhNC(Et)NPh}₂] has been determined.