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=CMe(2))(PPh(3))]ClO(4) (1:2) to give Rh(Cp)(mu-Cl)(NH=CMe(2))](2)(ClO(4))(2) (1), which in turn reacts with PPh(3) (1:2) to give Rh(Cp)Cl(NH=CMe(2))(PPh(3))]ClO(4) (2), and (ii) with Ag(NH=CMe(2))(2)]ClO(4) (1:2 or 1:4) to give Rh(Cp)Cl(NH=CMe(2))(2)]ClO(4) (3) or Rh(Cp)(NH=CMe(2))(3)](ClO(4))(2).H(2)O (4.H(2)O), respectively. Complex 3 reacts (i) with XyNC (1:1, Xy = 2,6-dimethylphenyl) to give Rh(Cp)Cl(NH=CMe(2))(CNXy)]ClO(4) (5), (ii) with Tl(acac) (1:1, acacH = acetylacetone) or with Au(acac)(PPh(3))] (1:1) to give Rh(Cp)(acac)(NH=CMe(2))]ClO(4) (6), (iii) with Ag(NH=CMe(2))(2)]ClO(4) (1:1) to give 4, and (iv) with (PPN)Cl (1:1, PPN = Ph(3)P=N=PPh(3)) to give Rh(Cp)Cl(imam)]Cl (7.Cl), which contains the imam ligand (N,N-NH=C(Me)CH(2)C(Me)(2)NH(2) = 4-imino-2-methylpentan-2-amino) that results from the intramolecular aldol-type condensation of the two acetimino ligands. The homologous perchlorate salt (7.ClO(4)) can be prepared from 7.Cl and AgClO(4) (1:1), by treating 3 with a catalytic amount of Ph(2)C=NH, in an atmosphere of CO, or by reacting 4with (PPN)Cl (1:1). The reactions of 7.ClO(4) with AgClO(4) and PTo(3) (1:1:1, To = C(6)H(4)Me-4) or XyNC (1:1:1) give Rh(Cp)(imam)(PTo(3))](ClO(4))(2).H(2)O (8) or Rh(Cp)(imam)(CNXy)](ClO(4))(2) (9), respectively. The crystal structures of 3 and 7.Cl have been determined.