화학공학소재연구정보센터
Inorganic Chemistry, Vol.45, No.1, 181-188, 2006
The first acetimino complexes of Rh(III). 4-Imino-2-methylpentan-2-amino-Rh(III) complexes through metal-assisted intramolecular aldol-type condensation of two acetimino ligands
[Rh(Cp*)Cl(mu-Cl)](2) (Cp-* = pentamethylcyclopentadienyl) reacts (i) with [Au(NH=CMe2)(PPh3)]ClO4 (1:2) to give [Rh(Cp-*)(mu-Cl)(NH=CMe2)](2)(ClO4)(2) (1), which in turn reacts with PPh3 (1:2) to give [Rh(Cp-*)Cl(NH=CMe2)(PPh3)]ClO4 (2), and (ii) with [Ag(NH=CMe2)(2)]ClO4 (1:2 or 1:4) to give [Rh(Cp-*)Cl(NH=CMe2)(2)]ClO4 (3) or [Rh(Cp-*)(NH=CMe2)(3)](ClO4)(2) center dot H2O (4 center dot H2O), respectively. Complex 3 reacts (i) with XyNC (1:1, Xy = 2,6-dimethylphenyl) to give [Rh(Cp-*)Cl(NH=CMe2)(CNXy)]ClO4 (5), (ii) with TI(acac) (1:1, acacH = acetylacetone) or with [Au(acac)-(PPh3)] (1:1) to give [Rh(Cp-*)(acac)(NH=CMe2)]ClO4 (6), (iii) with [Ag(NH=CMe2)(2)]ClO4 (1:1) to give 4, and (iv) with (PPN)Cl (1:1, PPN = Ph3P=N=PPh3) to give [Rh(Cp-*)Cl(imam)]Cl (7 center dot Cl), which contains the imam ligand (N,N-NH=C(Me)CH2C(Me)(2)NH2 = 4-imino-2-methylpentan-2-amino) that results from the intramolecular aldol-type condensation of the two acetimino ligands. The homologous perchlorate salt (7 center dot ClO4) can be prepared from 7 center dot Cl and AgClO4 (1:1), by treating 3 with a catalytic amount of Ph2C=NH, in an atmosphere of CO, or by reacting 4 with (PPN)Cl (1:1). The reactions of 7 center dot ClO4 with AgClO4 and PTo(3) (1:1:1, To = C6H4He-4) or XyNC (1:1:1) give [Rh(Cp-*)(imam)(PTo(3))](ClO4)(2) center dot H2O (8) or [Rh(Cp-*)(imam)(CNXy)](ClO4)(2) (9), respectively. The crystal structures of 3 and 7 center dot Cl have been determined.