160928-18-7Relevant academic research and scientific papers
Synthesis, characterization, and reactivity of heterodinuclear RuM (M = Cu(I), Ag(I), Au(I), Rh(I), and Ir(I)) and heterotrinuclear RuAg2 and RuRhAg compounds derived from the metal-complex ligand bis(pyrazolato)(p-cymene)(pyrazole)ruthenium(II)
Carmona, Daniel,Ferrer, Joaquina,Atencio, Reinaldo,Lahoz, Fernando J.,Oro, Luis A.,Lamata, María Pilar
, p. 2057 - 2065 (1995)
The reaction of the mononuclear ruthenium p-cymene pyrazolate complex [(η6-p-cymene)-Ru(pz)2(Hpz)] (1) (p-cymene = p-isopropylmethylbenzene; Hpz = pyrazole, C3H4N2) with the halide triphenylphosphine complexes [MCl(PPh3)]x and KOH led to the corresponding heterodinuclear compounds [(η6-p-cymene)Ru(pz)3M(PPh3)] (M = Cu (2), Ag (3), Au (4)). In solution, complexes 2-4 showed a dynamic behavior consisting of exchange between terminal and bridging pyrazolate groups accompanied by dissociation of the phosphine ligand. Complex 3 reacted with AgBF4 and PPh3 to yield the heterotrinuclear RuAg2 complex [(η6-p-cymene)Ru(μ-pz)3{Ag(PPh3)} 2]BF4 (5) which was also fluxional. Heterodinuclear derivatives of formula [(η6-p-cymene)(pz)Ru(μ-pz)2ML2] (M = Rh; L2 = 1,5-cyclooctadiene (COD) (6), (CO)2 (7). M = Ir; L2 = (CO)2 (8)) have been prepared by treating complex 1 with the appropriate [M(acac)L2] (acac = acetylacetonate) compounds. The carbonyl complexes 7 and 8 reacted with mono- or diphosphines, rendering [(η6-p-cymene)(pz)Ru(μ-pz)2ML2] (M = Rh; L2 = CO, PPh3 (9), CO, P(OMe)3 (10), CO, bis(diphenylphosphino)methane (dppm) (11), dppm (14), 1,2-bis(diphenylphosphino)ethane (dppe) (15), cis-1,2-bis(diphenylphosphino)ethylene (dppen) (16), (R)-(+)-1,2-bis(diphenylphosphino)propane (R-prophos) (17a,b). M = Ir; L2 = CO, PPh3 (12), CO, dppm (13), dppe (18)). Protonation of 6-9 and 12 with HBF4 afforded the corresponding cationic complexes [(η6-p-cymene)(Hpz)Ru(μ-pz)2ML2]BF 4 (M = Rh; L2 = COD (19), (CO)2 (20), CO, PPh3 (21). M = Ir; L2 = (CO)2 (22), CO, PPh3 (23)). The molecular structure of complex 22 has been determined by X-ray diffraction methods. Crystals are monoclinic, space group P21/c, with cell parameters a = 7.9909(6) A?, b = 17.0590(9) A?, c = 19.083(2) A?, β = 93.94(1)°, and Z = 4. The molecule exhibits two bridging pyrazolate groups between the metals. No direct intermetallic interaction is observed, the Ru?Ir distance being 3.6770(6) A?. In the solid state, a clear hydrogen bond is present between one fluorine atom of the tetrafluoroborate anion and the pyrazole ligand. The heterotrinuclear RuRhAg cationic derivatives [(η6-p-cymene)Ru{(μ-pz)Ag(PPh3)}{(μ-pz) 2RhL2}]BF4 (L2 = COD (24), CO, PPh3 (25)) have been prepared on the addition of equimolar amounts of AgBF4 and PPh3 to complexes 6 and 9, respectively.
