α‐Dialdimine Complexes of Rhodium(I) and Iridium(I): Their Reactivity with Dioxygen and Dihydrogen

The rhodium(I) and iridium(I) complexes [M(Cl){ArN=C(H)C(H)=NAr}(CNtBu)] (1: M = Rh, Ar = 2,6-iPr2C6H3; 2: M = Rh, Ar = Mes; 3: M = Ir, Ar = Mes; Mes = 2,4,6-Me3C6H2) have been prepared by the reaction of [M(μ-Cl)(coe)2]2 (M = Rh, Ir; coe = cyclooctene) with the α-dialdimines ArN=C(H)C(H)=NAr (Ar = 2,6-iPr2C6H3, Mes) in thf, followed by the addition of CNtBu. XANES spectra and DFT calculations on 2 and 3 suggest an oxidation state +I at the metal centers. Treatment of the complexes 2 and 3 with O2 or 18O2 gave the peroxido complexes [M(Cl)(O2){MesN=C(H)C(H)=NMes}(CNtBu)] (4a: M = Rh; 5a: M = Ir) and [M(Cl)(18O2){MesN=C(H)C(H)=NMes}(CNtBu)] (4b: M = Rh; 5b: M = Ir). The reaction of 3 with dihydrogen resulted in the formation of the iridium dihydrido complex [Ir(Cl)(H)2{MesN=C(H)C(H)=NMes}(CNtBu)] (6a). Two isomeric α-imine-amine complexes [Ir(Cl)(H)2{MesN(H)CH2C(H)=NMe}(CNtBu)] (7/7′) were obtained after prolonged reaction under H2. All of the complexes were characterized by NMR and IR spectroscopy. In addition, complexes 2, 3,and 7 were characterized by X-ray crystallography.