On the Reactivity Toward Ketones of New Methyl Amino Complexes of Rh(lll) and Ag(l). Synthesis of Ortho-Rhodiated Acetophenone Methyl Imine Complexes.

MeNH2 reacts with silver salts AgX (2:1) to give [Ag(NH2Me)2]X [X = TfO = CF3SO3 (1·TfO) and ClO4 (1·ClO4)]. Neutral mono(amino) Rh(lll) complexes [Rh(Cp*)Cl2(NH2R)] [R = Me (2a), To C6H4Me-4 (2b)] have been prepared by reacting [Rh(Cp*)Cl(μ-Cl)]2 with RNH2 (1:2). The following cationic methyl amino complexes have also been prepared: [Rh(Cp*)Cl(NH2Me)(PPh3)]TfO (3·TfO), from [Rh(Cp*)Cl2(PPh3)] and 1·TfO (1:1); [Rh(Cp*)Cl(NH2R)2]X, where R = Me, X = Cl, (4aCI), from [Rh(Cp*)Cl(μ-Cl)]2 and MeNH2 (1:4), or R Me, X = ClO4 (4a·ClO4, from 4a·Cl and NaCIO4 (1:4.8), or R = To, X = TfO (4b·TfO), from [Rh(Cp*)Cl(μ-Cl)]2, ToNH2 and TITfO (1:4:2); [Rh(Cp*)(NH2Me)(tBubpy)](TfO)2 (tBubpy = 4,4′-di-tert-butyl-2,2′-bipyridine, 5·TfO), from 2a, TITfO and tBubpy (1:2:1); [Rh(Cp*)(NH2Me)3](TfO)2 (6·TfO) from [Rh(Cp*)Cl(μ0Cl)]2 and 1·TfO (1:4). 2–6 constitute the first family of methyl amino complexes of rhodium. 1 and 4a·CIO4 react with acetone to give, respectively, the methyl imino complexes [Ag{N(Me)=CMe2}2]X [X = TfO (7·TfO), ClO4 (7·ClO4)], and [Rh(Cp*)Cl(Me-imam)]ClO4 [8·ClO4, Me-imam = N,N′-N(Me)=C(Me)CH2C(Me)2NHMe). 7·X (X = TfO, ClO4) are new members of the small family of methyl acetimino complexes of any metal whereas 8·ClO4 results after a double acetone condensation to give the corresponding bis(methyl acetimino) complex and an aldol-like condensation of the two imino ligands. The acetimino complex [Ag(NH=CMe2)2]ClO4 reacts with [Rh(Cp*)Cl(imam)]ClO4 [1:1, imam = N,N′-NH=C(Me)CH2C(Me)2NH2] to give [Rh(Cp′)(imam)(NH=CMe2)](ClO4)2 (9a·ClO4). 8·ClO4 reacts with AgCIO4 (1:1) in MeCN to give [Rh(Cp*)-(Me-imam)(NCMe)](ClO4)2 (9b·ClO4), which in turn reacts with XyNC (Xy = C6H3Me2-2,6) or with MeNH2 (1:1) to give [Rh(Cp′)(Me-imam)L](ClO4)2 [L = XyNC (9c·ClO4), MeNH2 (9d-ClO4)] 6·TfO reacts with acetophenone to give [Rh(Cp*){C,N-C6H4C(Me)=N(Me)-2}(NH2Me)]TfO (10a·TfO), the first complex resulting from such a condensation and cyclometalation reaction. In turn, 10a·TfO reacts with isocyanides RNC (1:1) at room temperature to give [Rh(Cp*){C,N,C6H4C(Me)=NMe-2}(CNR)]TfO [R = tBu (10b·TfO), Xy (10c-TfO)], or 1:12 at 60 °C to give [Rh-(Cp*){C,N-C(=NXy)C6H4C(Me)=N(Me)-2}(CNXy)]TfO (11·TfO). The crystal structures of 9a·CIO4-acetone-d6, 9c·ClO4, and 10a·TfO have been determined. [ABSTRACT FROM AUTHOR]