Rhodium(I) and Iridium(I) Complexes of Ferrocenyl-Functionalized Amidinates and Bis(amidinates): κ2N-Coordination Versus Ferrocenyl Ortho-Metalation

Abstract

The synthesis and characterization of two bulky ferrocenyl-functionalized amidinates and their lithium, potassium, rhodium(I), and iridium(I) complexes are reported. The ferrocenyl mono(amidine) [Fc{C(NDipp)(NHDipp)}] (1) (Fc = ferrocenyl; Dipp = 2,6-diisopropylphenyl) and its potassium complex [Fc{C(NDipp)2K}·3THF] (2) as well as the 1,1′-ferrocendiyl-bridged bis(amidinate) [fc{C(NMes)2Li}2·3THF] (3) (fc = ferrocene-1,1′-diyl; Mes = mesityl) were synthesized. Salt metathesis reactions with the metal precursors [Rh(cod)Cl]2 (cod = 1,5-cyclooctadiene) and [Ir(cod)Cl]2 gave the rhodium(I) and iridium(I) complexes [Fc{C(NDipp)2Rh(cod)}] (4), [fc{C(NMes)2Rh(cod)}2] (5), and [fc{C(NMes)2Ir(cod)}2] (6), as well as the ortho-metalated compound [(Cp)Fe(C5H3){C(NHDipp)(NDipp)Ir(cod)}] (7). As complex 7 showed an ortho-metalation on the ferrocene backbone, we investigated this reaction in more detail. It was found that the rhodium(I) complexes 4 and 5 also undergo ortho-metalation upon treatment with carbon monoxid...