Rhodium (III)-cyclometalated-imine complexes : solution behavior and reactivity with molecular hydrogen

摘要: Acetone solutions of cis,trans,cis-[Rh(H)2(PPh3)2(acetone)2]PF6 and cis-[Rh(PPh3)2(acetone)2]PF6 react with the imines RNCR‘(R‘ ‘), where R = PhCH2, Ph, or C6H11; R‘ H Me; R‘ ‘ Ph p-OMe-C6H4, to form orthometalated complexes exemplified by [Rh(H){RNCR‘(o-C6H4)}(PPh3)2(acetone)]PF6 that are generally characterized spectroscopically, in one case (where Me, p-OMe-C6H4) X-ray crystallography. These maintain their integrity acetone solution show no reaction toward 1 atm H2 at ambient conditions. In MeOH, which Me simply change corresponding MeOH derivative, but when they partially converted non-orthometalated, η1-N-imine species [Rh(PPh3)2(RNCHR‘ ‘)(MeOH)]PF6 (I), stoichiometric hydrogenation imine amine occurs via I. We have shown recently (Inorg. Chem. 2004, 43, 4820) catalyzed PhCH2NC(H)Ph dibenzylamine using cis,trans,cis-[Rh(H...