Browsing by Author "Viguri, F"

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    Bis(diphenylphosphino)amine and their dichalcogenide derivatives as ligands in rhodium(III), iridium(III), and ruthenium(II) complexes.: Crystal structures of [(η5-C5Me5)MCl{η2-(SePPh2)2N}] (M = Rh, Ir)
    (2000) Valderrama, M; Contreras, R; Lamata, MP; Viguri, F; Carmona, D; Lahoz, FJ; Elipe, S; Oro, LA
    Reaction of the dimers [{(eta(5)-C5Me5)MCl}(2)(mu-Cl)(2)] (M = Rh, Ir) or [{(eta(6)-arene)RuCl}(2)(mu-Cl)(2)] (arene = p-(MeC6H4Pr)-Pr-i, C6Me6) with NH(PPh2)(2) in the presence of AgA (A = BF4, PF6) leads to the mononuclear cationic complexes [(eta(5)-C5Me5)MCl{eta(2)- (PPh2)(2)NH}]A (M = Rh (1), Ir (2)) or [(eta(6)-arene)RuCl{eta(2)-(PPh2)(2)NH}]A (arene = p-(MeC6H4Pr)-Pr-i (3), C6Me6 (4)). Similar reactions using the chalcogenide derivatives NH(EPPh2)(2) (E = S, Se) yield the neutral complexes [(eta(5)-C5Me5)RhCl{eta(2)-(EPPh2)(2)N}] (E = S (5), Se (6)), [(eta(5)-C5Me5)IrCl{eta(2)-(EPPh2)(2)N}] (E = S (7), Se (8)), [(eta(6)-arene)RuCl{eta(2)-(SPPh2)(2)N}] (arene = C6H6 (9), p-(MeC6H4Pr)-Pr-i (10)) and [(eta(6)-arene)RuCl{eta(2)-(SePPh2)(2)N)}] (arene = C6Me6 (11), p-(MeC6H4Pr)-Pr-i (12)). Chloride abstraction from complexes 5-8 with AgPF6 in the presence of PPh3 gives the cationic complexes [(eta(5)-C5Me5)Rh{eta(2)-(EPPh2)(2)N}(PPh3)]PF6 (E = S (13), Se (14)) and [(eta(5)-C5Me5)Ir{eta(2)-(EPPh2)(2)N}(PPh3)]PF6 (E = S (15), Se (16)). Complexes 13-16 can also be synthesised from the starting dinuclear complexes, AgPF6, NH(EPPh2)(2) and PPh3. Using this alternative synthetic route the related ruthenium complexes [(eta(6)-C6Me6)Ru{eta(2)-(EPPh2)(2)N}(C5H5N)] BF4 (E = S (17), Se (18)) can be prepared. All described compounds have been characterised by microanalysis and NMR (H-1, P-31) and IR spectroscopy. The crystal structures of the neutral complexes [(eta(5)-C5Me5)MCl{eta(2)-(SePPh2)(2)N}] (M = Rh (6), Ir (8)) have been determined by X-ray diffraction methods. Both complexes exhibit analogous pseudo-octahedral molecular structures with a C5Me5 group occupying three coordination positions and a bidentate chelate Se,Se'-bonded ligand and a chloride atom completing the coordination sphere. (C) 2000 Elsevier Science S.A. All rights reserved.
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    Syntheses and characterization of binuclear Rh-2, Ir-2 and RhIr complexes containing dimethyl phosphonate and pyrazolate bridging ligands
    (ROYAL SOC CHEMISTRY, 1996) Valderrama, M; Cuevas, J; Boys, D; Carmona, D; Lamata, MP; Viguri, F; Atencio, R; Lahoz, FJ; Oro, LA
    The reaction of [Ir(eta(5)-C(5)Me(5))I{PO(OMe)(2)}{P(OH)OMe)(2)}] with pyrazole (Hpz) in the presence of AgPF6 gave [Ir(eta(5)-C(5)Me(5)){PO(OMe)(2)}{P(OH)(OMe)(2)}(Hpz)]PF6 1. Deprotonation of 1 with sodium carbonate afforded the neutral compound [Ir(eta(5)-C(5)Me(5)){PO(OMe)(2)}(2)(Hpz)] 2 which, in turn, can be deprotonated to [(eta(5)-C(5)Me(5))Ir{PO(OMe)(2)}(2)(pz)M'] (M' = Tl 3 or Na 4) by Tl(acac) (acac = acetylacetonate) or NaH, respectively. The complex [Ir(eta(5)-C(5)Me(5))I-2{P(OH)(OMe)(2)}] 5, prepared by cleaving the iodide bridges in [{Ir(eta(5)-C(5)Me(5))I}(2)(mu-I)(2)] with HPO(OMe)(2), reacted with Hpz in the presence of AgPF6 to give [Ir(eta(5)-C(5)Me(5)){PO(OMe)(2)}(Hpz)(2)]PF6 6. Complexes of formulae [(eta(5)-C(5)Me(5))Ir{PO(OMe)(2)(pz)M '' L(2)][M '' L(2) = Rh(CO)(2) 7, Rh(cod) 8 or Ir(cod) 9] were prepared from 2 [Rh(acac)(CO)(2)] or from 3 and the appropriate [{M ''(cod)}(2)(mu-Cl)(2) dimer (cod = cycloocta-1,5-diene). Complex 6 reacted with [{Rh(cod)}(2)(mu-Cl)(2)] in basic medium to give [(eta(5)-C(5)Me(5))Ir{PO(OMe)(2)}(pz)(2)Rh(cod)] 10. The rhodium-thallium compound [(eta(5)-C(5)Me(5))Rh{PO(OMe)(2)}(2)(pz)Tl] or the in situ prepared sodium derivative [(eta(5)-C(5)Me(5))Rh{PO(OMe)(2)}(pz)(2)Na] reacted with the dimers [{M ''(diolefin)}(2)(mu-Cl)(2)] affording [(eta(5)-C(5)Me(5))Rh{PO(OMe)(2)}(2)(pz)M ''(diolefin) = [M ''(diolefin) = Ir(cod) 11 or Rh(nbd) 12] or [(eta(5)-C(5)Me(5)){PO(OMe)(2)}Rh(pz)(2)}Rh(pz)(2)M ''(diolefin)][M ''(diolefin) = Rh(cod) 13, Ir(cod) 14 or Rh(nbd) 15], respectively (nbd = bicyclo[2.2.1]hepta-2,5-diene). Related heterovalent complexes of general formula [I(eta(5)-C(5)Me(5))M{PO(OMe(2)}(2)M ''(diolefin)][M = Ir, M'(diolefin) = Rh(cod) 16 or Ir(cod) 17; M = Rh, M ''(diolefin) = Rh(cod) 18, Ir(cod) 19, or Rh(nbd) 20] have been prepared starting from the mononuclear complexes [M(eta(5)-C(5)Me(5))I{PO(OMe)(2)}{P(OH)(OMe)(2)}] (M = Ir or Rh). All the complexes have been characterized by spectroscopic of 8 by toluene-p-sulfonic acid is reported. The structures of 8 and 16 have been determined by X-ray diffraction methods. Both complexes consist of doubly bridged binuclear (C(5)Me(5))Ir-Rh(cod) species, where the Ir atoms exhibit pseudo-octahedral co-ordination and the rhodium square planar. The bridging system in 16 is formed by two identical P,O-bonded phosphonate groups, while in 8 a pyrazolate and a phosphonate ligand are bridging the metals. The intermetallic separations are 4.0445(9) (8) and 4.0928(9) Angstrom (16).
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    Tris(diphenylthiophosphinoyl)methanide as tripod ligand in rhodium(III), iridium(III) and ruthenium(II) complexes.: Crystal structures of [(η5-C5Me5)Ir{η3-(SPPh2)3C-S,S′,S"}]BF4 and [(η6-MeC6H4Pri)Ru{η3-(SPPh2)3C-S,S′,S"}]BPh4
    (1997) Valderrama, M; Contreras, R; Arancibia, V; Munoz, P; Boys, D; Lamata, MP; Viguri, F; Carmona, D; Lahoz, FJ; Lopez, JA; Oro, LA
    Reaction of the complex [{(eta(5)-C5Me5)RhCl2}(2)], in CH2Cl2 solution, with AgBF4 (1:2 molar ratio) and (SPPh2)(3)CH leads to the cationic compound [(eta(5)-C5Me5)RhCl{eta(2)-(SPPh2)(2)CH(SPPh2)-S,S'}]BF4 (1) which is deprotonated by thallium(I) pyrazolate affording [(eta(5)-C5Me5)Rh{eta(3)-(SPPh2)(3)C-S,S',S "}]BF4 (2a). The iridium dimer [{(eta(5)-C5Me5)IrCl2}(2)] reacts with silver salts and (SPPh2)(3)CH, in CH2Cl2 or Me2CO, under analogous conditions, affording mixtures of [(eta(5)-C5Me5)IrCl{eta(2)-(SPPh2)(2)CH(SPPh2)-S,S'}](+) and [(eta(5)-C5Me5)Ir{eta(3)-(SPPh2)(3)C-S,S',S "}]A [A = BF4- (3a), PF6- (3b)]. Addition of Et3N to the mixture gives pure complexes 3. The ruthenium complexes [{(eta(6)-arene)RuCl2}(2)] (arene = C6Me6, p-MeC6H4Pri) react with (SPPh2)(3)CH, in the presence of AgA (A = PF6- or BF4-) or Na BPh4, in CH2Cl2 or Me2CO, yielding only the deprotonated complexes [(eta(6)-arene)Ru{eta(3)-(SPPh2)(3)C-S,S',S "}]A [arene = C6Me6, A = BF4; arene = p-MeC6H4Pri, A = BPh4 (4a), PF6 (4b)]. The crystal structures of 3a and 4a were established by X-ray crystallography. Compound 3a crystallizes in the orthorhombic space group Pna2(1), with lattice parameters a = 41.477(6), b = 10.6778(11), c = 20.162(3) Angstrom and Z = 8. Complex 4a crystallizes in a monoclinic lattice, space group P2(1)/n, with a = 20.810(4), b = 12.555(3), c = 23.008(4) Angstrom, beta = 95.82(2)degrees and Z = 4. Both cationic complexes exhibit analogous pseudo-octahedral molecular structures with the anionic (SPPh2)(3)C- ligand bonded via the three sulphur atoms in a tripodal, tridentate fashion. Each metal centre completes its coordination environment with a eta(5)-C5Me5 (3a) or a eta(6)-MeC6H4Pri group (4a). A quite interesting result concerns the non-planarity of the methanide carbon which display P-C-P angles in the range 112.6-114.4(5)degrees in 3a and 111.9-113.6(4)degrees in 4a. The redox chemistry of the complexes was investigated by cyclic voltammetry. The Rh(III) complexes are quasi-reversibly reduced to Rh(I) and the Ir(III) complex is irreversibly reduced to Ir(I) in acetonitrile solutions. The Ru(II) complex undergoes a quasi-reversible reduction to Ru(I) and a reversible oxidation to Ru(III). (C) 1997 Elsevier Science S.A.