title: Synthesis and reactivity of the novel hydride derivative RhHCl(TIMP(3)) (HTIMP(3) = tris[1-(diphenylphosphino)-3-methyl-1H-indol-2-yl]methane).
abstract: The reaction of HTIMP(3) (HTIMP(3) = tris[1-(diphenylphosphino)-3-methyl-1H-indol-2-yl]methane) with [RhCl(COD)](2) and Rh(acac)(CO)(2) produces RhHCl(TIMP(3)) (1H) and Rh(TIMP(3))(CO) (2), respectively, both exhibiting tetradentate kappaC,kappa(3)P-coordination of the TIMP(3) moiety. The reaction of RhHCl(TIMP(3)) with nucleophiles (L) in the presence of AgBF(4) or AgPF(6) produces different compounds depending on the nature of L. Indeed, cationic Lewis adducts of formula [RhH(L)(TIMP(3))](+) ((2H+)-(5H+)) are obtained when L is CO, CNCH(2)Ph, pyridine or CH(2)CHCN. On the other hand, when the incoming nucleophile is CH(3)COOH the hydride-free complex [Rh(CH(3)COO)(TIMP(3))](+) ((6+)) is obtained. Finally, the reaction of RhHCl(TIMP(3)) with PhCCPh and CH(2)CHCOOMe in the presence of AgPF(6) leads to the insertion products [Rh(PhCCHPh)(TIMP(3))](+) ((+)) and [Rh(CH(2)CH(2)COOMe)(TIMP(3))](+) ((8+)), respectively. The solid state structure has been determined by single crystal X-ray diffraction in selected cases (1H, (6+)).
authors.affiliation: Instituto Ciencia Molecular, Universidad de Valencia, Polígono La Coma, s/n 46980, Paterna, Valencia, Spain.
authors.forename: Marco
authors.initials: M
authors.lastname: Ciclosi
authors.forename: Francisco
authors.initials: F
authors.lastname: Estevan
authors.forename: Pascual
authors.initials: P
authors.lastname: Lahuerta
authors.forename: Vincenzo
authors.initials: V
authors.lastname: Passarelli
authors.forename: Julia
authors.initials: J
authors.lastname: Pérez-Prieto
authors.forename: Mercedes
authors.initials: M
authors.lastname: Sanaú
mesh_terms: D018360:Crystallography, X-Ray; D008958:Models, Molecular; D015394:Molecular Structure; D009942:Organometallic Compounds / Q000138:chemical synthesis* / Q000737:chemistry*; D013237:Stereoisomerism
chemical_list: D009942:Organometallic Compounds; C540928:chlorohydrido(tris(1-(diphenylphosphino)-3-methyl-1H-indol-2-yl)methane)rhodium(II)