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 Jose ´ Vicente,* Marı ´a-Teresa Chicote,* Rita Guerrero, Inmaculada Vicente-Herna ´ ndez, and Miguel M. Alvarez-Falco ´n Grupo de Quı ´mica Organometa ´ lica, Departamento de Quı ´mica Inorga ´ nica, UniVersidad de Murcia, Aptdo. 4021, Murcia, 30071 Spain Received September 6, 2005 [Rh(Cp*)Cl(µ-Cl)] 2 (Cp* ) pentamethylcyclopentadienyl) reacts (i) with [Au(NHdCMe 2 )(PPh 3 )]ClO 4 (1:2) to give [Rh(Cp*)(µ-Cl)(NHdCMe 2 )] 2 (ClO 4 ) 2 (1), which in turn reacts with PPh 3 (1:2) to give [Rh(Cp*)Cl(NHdCMe 2 )(PPh 3 )]- ClO 4 (2), and (ii) with [Ag(NHdCMe 2 ) 2 ]ClO 4 (1:2 or 1:4) to give [Rh(Cp*)Cl(NHdCMe 2 ) 2 ]ClO 4 (3) or [Rh(Cp*)- (NHdCMe 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(NHdCMe 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)(NHdCMe 2 )]ClO 4 (6), (iii) with [Ag(NHdCMe 2 ) 2 ]ClO 4 (1:1) to give 4, and (iv) with (PPN)Cl (1:1, PPN ) Ph 3 PdNdPPh 3 ) to give [Rh(Cp*)Cl(imam)]Cl (7‚Cl), which contains the imam ligand (N,N-NHdC(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 CdNH, in an atmosphere of CO, or by reacting 4 with (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. Introduction Acetimine, one of the condensation products of acetone and ammonia, 1 is an unstable compound that decomposes after short periods of storage to give acetonine (2,2,4,4,6- pentamethyl-2,3,4,5-tetrahydropyrimidine). 2 The difficulties associated with the preparation and handling of acetimine 3 may account for the scarcity of complexes with this ligand. In fact, acetimine itself has never been used in the various syntheses of the metal-acetimino complexes reported so far. 4-8 The synthesis by us of [Au(NHdCMe 2 )(PPh 3 )]ClO 4 6 and [Ag(NHdCMe 2 ) 2 ]ClO 4 8 prompted us to check if they could transmetalate the acetimine ligand(s) to different metal complexes, thus providing a general method for preparing acetimino complexes. In fact, using [Ag(NHdCMe 2 ) 2 ]ClO 4 , * To whom correspondence should be addressed. E-mail: jvs1@um.es (J.V.), mch@um.es (M.-T.C.). (1) Bradbury, R. B.; Hancox, N. C.; Hatt, H. H. J. Chem. Soc. 1947, 1394. Murayama, K.; Morimura, S.; Amakasu, O.; Toda, T.; Yamao, E. Nippon Kagaku Zasshi 1969, 90, 296 (Chem. Abstr. 1969, 70, 324). (2) Findeisen, K.; Heitzer, H.; Dehnicke, K. Synthesis 1981, 702. (3) Verardo, G.; Giumanini, A. G.; Strazzolini, P.; Poiana, M. Synth. Commun. 1988, 18, 1501. Xu, T.; Zhang, J.; Haw, J. F. J. Am. Chem. Soc. 1995, 117, 3171. (4) Sellmann, D.; Thallmair, E. J. Organomet. Chem. 1979, 164, 337. Harman, W. D.; Taube, H. Inorg. Chem. 1988, 27, 3261. Rappert, T.; Yamamoto, A. Chem. Lett. 1994, 2211. Fischer, E. O.; Knauss, L. Chem. Ber. 1970, 103, 1262. Czarkie, D.; Shvo, Y. J. Organomet. Chem. 1970, 280, 123. Wong, K.-Y.; Che, C.-M.; Li, C.-K.; Chiu, C.-K.; Zhou, Z.-Y.; Mak, T. C. W. Chem. Commun. 1992, 754. Adcock, P. A.; Keene, F. R.; Smythe, R. S.; Snow, M. R. Inorg. Chem. 1984, 23, 2336. Yeh, W. Y.; Ting, C. S.; Peng, S. M.; Lee, G. H. Organometallics 1995, 14, 1417. Castarlenas, R.; Esteruelas, M. A.; On ˜ate, E. Organometallics 2000, 19, 5454. Klingebiel, W.; Nolte- meyer, M.; Schmidt, H.-G.; Schmidt-Ba ¨se, D. Chem. Ber./Recl. 1997, 130, 753. Aresta, M.; Quaranta, E.; Dibenedetto, A.; Giannoccaro, P.; Tommasi, I.; Lanfranchi, M.; Tiripicchio, A. Organometallics 1997, 16, 834. King, R. B.; Douglas, W. M. Inorg. Chem. 1974, 13, 1339. Fornie ´s, J.; Casas, J. M.; Martı ´n, A.; Rueda, A. J. Organometallics 2002, 21, 4560. (5) Vicente, J.; Chicote, M. T.; Guerrero, R.; Vicente-Herna ´ndez, I.; Alvarez-Falco ´n, M. M.; Jones, P. G.; Bautista, D. Organometallics 2005, 24, 4506. (6) Vicente, J.; Chicote, M. T.; Guerrero, R.; Saura-Llamas, I. M.; Jones, P. G.; Ramı ´rez de Arellano, M. C. Chem.sEur. J. 2001, 7, 638. Inorg. Chem. 2006, 45, 181-188 10.1021/ic051521w CCC: $33.50 © 2006 American Chemical Society Inorganic Chemistry, Vol. 45, No. 1, 2006 181 Published on Web 11/17/2005