alpha-Dialdimine Complexes of Rhodium(I) and Iridium(I): Their Reactivity with Dioxygen and Dihydrogen

作者：Eissler Anna; Klaering Paul; Emmerling Franziska; Braun Thomas^*

来源：European Journal of Inorganic Chemistry, 2013, 2013(27): 4775-4788.

DOI：10.1002/ejic.201300625

• Rhodium
• Iridium
• Aldimines
• Peroxido ligands
• Hydrido ligands

The rhodium(I) and iridium(I) complexes [M(Cl){ArN=C(H)C(H)=NAr}(CNtBu)] (1: M = Rh, Ar = 2,6-iPr(2)C(6)H(3); 2: M = Rh, Ar = Mes; 3: M = Ir, Ar = Mes; Mes = 2,4,6-Me3C6H2) have been prepared by the reaction of [M(-Cl)(coe)(2)](2) (M = Rh, Ir; coe = cyclooctene) with the -dialdimines ArN=C(H)C(H)=NAr (Ar = 2,6-iPr(2)C(6)H(3), 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 O-2 or O-18(2) gave the peroxido complexes [M(Cl)(O-2){MesN=C(H)C(H)=NMes}(CNtBu)] (4a: M = Rh; 5a: M = Ir) and [M(Cl)(O-18(2)){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 -imine-amine complexes [Ir(Cl)(H)(2){MesN(H)CH2C(H)=NMe}(CNtBu)] (7/7) were obtained after prolonged reaction under H-2. All of the complexes were characterized by NMR and IR spectroscopy. In addition, complexes 2, 3,and 7 were characterized by X-ray crystallography.

• 出版日期2013-9-10