Iridium(III)-(hydrido)cyclometallated-imine complexes and metal-promoted hydrolytic cleavage of imines

摘要

The room temperature reaction of the complex cis,trans,cis-[Ir(H)_2(PPh_3)_2(Solv)_2]PF_6(Solv is a solvent) with the imine PhCH_2N=CHPh in acetone generates (with loss of H_2) the orthometallated complex [Ir(H){PhCH_2N=CH(o-C_6H_4)}(PPh_3)_2(Me_2CO)]PF_6 (3) containing a five-membered cyclometallated imine moiety.In MeOH,the reaction at an imine:Ir ratio=1 leads to the corresponding MeOH analog of 3,while with excess imine,the mixed orthometallated imine/bezylamine complex [Ir(H){PhCH_2N=CH(o-C_6H_4)}(PPh_3)_2(PhCH_2NH_2)]PF_6 (4) is formed;the source of the coordinated amine is an Ir-promoted hydrolysis of the imine,the water likely coming from imine.Complexes 3 and 4 are fully characterized by elemental analysis,~1H and ~(31)P{~1H} NMR spectroscopy,and X-ray crystal structure analysis.