On the Reactivity Toward Ketones of New Methyl Amino Complexes of Rh(III) and Ag(I). Synthesis of Ortho-Rhodiated Acetophenone Methyl Imine Complexes † (original) (raw)

2007, Inorganic Chemistry

MeNH 2 reacts with silver salts AgX (2:1) to give [Ag(NH 2 Me) 2 ]X [X ) TfO ) CF 3 SO 3 (1‚TfO) and ClO 4 (1‚ClO 4 )]. Neutral mono(amino) Rh(III) complexes [Rh(Cp*)Cl 2 (NH 2 R)] [R ) Me (2a), To ) C 6 H 4 Me-4 (2b)] have been prepared by reacting [Rh(Cp*)Cl(µ-Cl)] 2 with RNH 2 (1:2). The following cationic methyl amino complexes have also been prepared: [Rh(Cp*)Cl(NH 2 Me)(PPh 3 )]TfO (3‚TfO), from [Rh(Cp*)Cl 2 (PPh 3 )] and 1‚TfO (1:1); [Rh(Cp*)Cl(NH 2 R) 2 ]X, where R ) Me, X ) Cl, (4a‚Cl), from [Rh(Cp*)Cl(µ-Cl)] 2 and MeNH 2 (1:4), or R ) Me, X ) ClO 4 (4a‚ClO 4 ), from 4a‚Cl and NaClO 4 (1:4.8), or R ) To, X ) TfO (4b‚TfO), from [Rh(Cp*)Cl(µ-Cl)] 2 , ToNH 2 and TlTfO (1:4:2); [Rh(Cp*)(NH 2 Me)( t Bubpy)](TfO) 2 ( t Bubpy ) 4,4′-di-tert-butyl-2,2′-bipyridine, 5‚TfO), from 2a, TlTfO and t Bubpy (1: 2:1); [Rh(Cp*)(NH 2 Me) 3 ](TfO) 2 (6‚TfO) from [Rh(Cp*)Cl(µ-Cl)] 2 and 1‚TfO (1:4). 2−6 constitute the first family of methyl amino complexes of rhodium. 1 and 4a‚ClO 4 react with acetone to give, respectively, the methyl imino complexes [Ag{N(Me)dCMe 2 } 2 ]X [X ) TfO (7‚TfO), ClO 4 (7‚ClO 4 )], and [Rh(Cp*)Cl(Me-imam)]ClO 4 [8‚ClO 4 , Meimam ) N,N′-N(Me)dC(Me)CH 2 C(Me) 2 NHMe]. 7‚X (X ) TfO, ClO 4 ) are new members of the small family of methyl acetimino complexes of any metal whereas 8‚ClO 4 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(NHdCMe 2 ) 2 ]ClO 4 reacts with [Rh(Cp*)Cl(imam)]ClO 4 [1:1, imam ) N,N′-NHdC(Me)CH 2 C(Me) 2 NH 2 ] to give [Rh(Cp*)(imam)(NH)CMe 2 )](ClO 4 ) 2 (9a‚ClO 4 ). 8‚ClO 4 reacts with AgClO 4 (1:1) in MeCN to give [Rh(Cp*)-(Me-imam)(NCMe)](ClO 4 ) 2 (9b‚ClO 4 ), which in turn reacts with XyNC (Xy ) C 6 H 3 Me 2 -2,6) or with MeNH 2 (1:1) to give [Rh(Cp*)(Me-imam)L](ClO 4 ) 2 [L ) XyNC (9c‚ClO 4 ), MeNH 2 (9d‚ClO 4 )]. 6‚TfO reacts with acetophenone to give [Rh(Cp*){C,N-C 6 H 4 C(Me)dN(Me)-2}(NH 2 Me)]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-C 6 H 4 C(Me)dNMe-2}(CNR)]TfO [R ) t Bu (10b‚TfO), Xy (10c‚TfO)], or 1:12 at 60°C to give [Rh-(Cp*){C,N-C(dNXy)C 6 H 4 C(Me)dN(Me)-2}(CNXy)]TfO (11‚TfO). The crystal structures of 9a‚ClO 4 ‚acetone-d 6 , 9c‚ ClO 4 , and 10a‚TfO have been determined. Heitzer, H.; Deehnicke, K. Synthesis 1981, 702. (3) Vicente, J.; Chicote, M. T.; Guerrero, R.; Saura-Llamas, I. M.; Jones, P. G.; Ramírez de Arellano, M. C. Chem.sEur. J. 2001, 7, 638. (4) Vicente, J.; Chicote, M.-T.; Abrisqueta, M.-D.; Guerrero, R.; Jones, P. G. Angew. Chem., Int. Ed. Engl. 1997, 36, 1203. Vicente, J.; Chicote, M. T.; Guerrero, R.; Ramírez de Arellano, M. C. Chem.