Rhodium and Iridium Complexes with α‐Diketimine Ligands: Oxidative Addition of H 2 and O 2

The treatment of [M(μ‐Cl)(coe) 2 ] 2 (M = Rh, Ir; coe = cyclooctene) with the α‐diketimines ArN=C(Me)C(Me)=NAr (Ar = Ph, Xy; Xy = 2,6‐Me 2 C 6 H 3 ) in thf, followed by the addition of CN t Bu, gave the α‐diketimine complexes [M(Cl){ArN=C(Me)C(Me)=NAr} (CN t Bu)] ( 1 : M = Rh, Ar = Ph; 2 : M = Rh, Ar = Xy; 3 : M = Ir, Ar = Xy). The reaction of 3 with dihydrogen resulted in the formation of the iridium dihydrido complex [Ir(Cl)(H) 2 {XyN=C(Me)C(Me)=NXy}(CN t Bu)] ( 4 ). The complexes 2 and 3 reacted with O 2 or 18 O 2 to yield the peroxido complexes [M(Cl)(O 2 ){XyN=C(Me)C(Me)=NXy}(CN t Bu)] ( 5a : M = Rh; 6a : M = Ir) and [M(Cl)( 18 O 2 ){XyN=C(Me)C(Me)=NXy}(CN t Bu)] ( 5b : M = Rh; 6b : M = Ir), respectively. All of the complexes were characterized by NMR and IR spectroscopy. In addition, complexes 3 and 5a were characterized by X‐ray crystallography.