Browsing by Author "Boys, D"

Now showing 1 - 13 of 13
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    Bis(diphenylphosphino)methylamine as chelate ligand in pentamethylcyclopentadienylrhodium(III) and iridium(III) complexes.: Crystal structure of [(η5-C5Me5)RhCl(η2-P,P′-(PPh2)2NMe}]BF4
    (2003) Valderrama, M; Contreras, R; Boys, D
    Reactions of the dimers [{(eta(5) -C5Me5)MCl(mu-Cl)}(2)] (M = Rh, Ir) with the ligand NMe(PPh2)(2) in 1:2 molar ratio afford the mononuclear cationic complexes [(eta(5)-C5Me5)MCl{eta(2)-P,P'-(Ph2P)(2)NMe}]Cl (M = Rh 1, Ir 2). Similar iodide complexes, [(eta(5)- C5Me5)MCl{eta(2)-P,P'-(Ph2P)(2)NMe}]I (M = Rh 3, Ir 4), can be prepared by N-functionalization of co-ordinated dppa ligand in complexes [(eta(5) -C5Me5)MCl{eta(2)-P,P'-(Ph2P)(2)NH}]BF4. The tetrafluoroborate derivatives, [(eta(5)-C5Me5)MCl{eta(2)-P,P'- (Ph2P)(2)NMe}]BF4 (M = Rh 5, Ir 6) are prepared by reaction of complexes 1-4 with AgBF4 in acetone. All the compounds described are characterised by microanalysis, IR and NMR (H-1, P-31{H-1}) spectroscopy. The crystal structure of complex 5 is determined by X-ray diffraction methods. The complex exhibits a pseudo-octahedral molecular structure with a C5Me5 group occupying three co-ordination positions and a bidentate chelate P,P'-bonded ligand and a chloride atom completing the coordination sphere. (C) 2002 Elsevier Science B.V. All rights reserved.
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    C-Pt(IV) activation in new trimethylplatinum(IV) complexes: nucleophilic attack at metal-carbon bond
    (ELSEVIER SCIENCE SA, 2003) Romero, P; Valderrama, M; Contreras, R; Boys, D
    Reaction of the tetranuclear complex [Me3PtI](4) with the ligand o-Ph2P(E)C6H4SMe (E = S, Se) in a 1:4 molar ratio yields the mononuclear neutral complexes [Me3PtI(eta(2)-MeSC6H4P(E)Ph-2-S,S)] (E = S(1), Se(2)). Iodide abstraction from these compounds with AgPF6 in the presence of a ligand L (PPh3, py) leads to cationic complexes of the type [Me3Pt(eta(2)-MeSC6H4P(E)Ph-2-E,S)L]PF6 [E = S, L = PPh3 (3), Py (4); E = Se, L = Py (5)]. However, using complex 2 and the ligand PPh3 under identical conditions induces a reductive elimination reaction affording the Pt(II) complex [MePt(eta(2)-MeSC6H4PPh2-P,S)(PPh3)]PF6 (6). Reactions of complexes 3 and 4 with NaI reveal a nucleophilic attack of the iodide to one of the methyl groups bonded to the platinum center generating a series of subsequent side reactions. Complex [Me3Pt{eta(2)-MeSC6H4P(S)Ph-2-S,S}(py)]PF6.CH2Cl2 (4) was additionally characterised by X-ray diffraction. The platinum atom exhibits a distorted octahedral coordination, bonded to three methyl carbon atoms in a facial arrangement; a bidentate chelate S,S'-bonded ligand and a nitrogen atom of the pyridine ligand complete the metal coordination sphere. (C) 2003 Elsevier Science B.V. All rights reserved.
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    Diphenylphosphino(phenylthio)methane as a monodentate or bidentate chelate ligand in rhodium, iridium and ruthenium complexes, crystal structure of [(eta(5)-C(5)Me(5)) IrCl(eta(2)-Ph(2)PCH(2)SPh-P,S)]BF4 center dot Me(2)CO
    (1997) Valderrama, M; Contreras, R; Boys, D
    Reactions of complexes [{(eta(5)-C(5)Me(5))MCl(2)}(2)] (M = Rh, Ir) and [{(eta(6)-MeC(6)H(4)Pr(i))RuCl2}(2)] with the ligand Ph(2)PCH(2)SPh in acetone solution led to neutral complexes with the general formula [(ring)MCl(2)(eta(1)-Ph(2)PCH(2)SPh-P)] (1-3). These compounds react with thallium tetrafluoroborate in acetone solution to yield new cationic complexes in which the ligand is acting in its chelate P,S-donor fashion, [(ring)MCl(eta(2)Ph(2)PCH(2)SPh-P,S)]BF4 (4-6). When the removal of the chloride ligand in complexes 1-3 was carried out in the presence of a stoichiometric amount of Ph(2)PCH(2)SPh, cationic compounds containing two P-donor monodentate ligands of the type [(eta(5)-C(5)Me(5))MCl(eta(1)-Ph(2)PCH(2)SPh-P)(2)]BF4 (7 and 8) were obtained. The structure of the iridium derivative [(eta(5)-C(5)Me(5))IrCl(eta(2)-Ph(2)PCH(2)SPh-P,S)]BF4 . Me(2)CO has been determined by single-crystal X-ray diffraction methods. The complex cation contains a C(5)Me(5) group occupying three coordination positions of a distorted octahedral iridium centre, a bidentate chelate P,S-bonded ligand and a chloride atom completing the coordination sphere. (C) 1997 Elsevier Science Ltd.
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    Platinum(II) complexes with dithiolates and phosphinites as ligands: Crystal structure of [Pt{S2CO}{P(OMe)Ph(2)}(2)]
    (PERGAMON-ELSEVIER SCIENCE LTD, 1996) Contreras, R; Valderrama, M; Riveros, O; Moscoso, R; Boys, D
    Reaction of the complex [PtCl{P(O)Ph(2)} {P(OH)Ph(2)}(2)] with silver or thallium derivatives of dithiolate ligands led to neutral complexes of general formula [Pt{S-S} {P(O)Ph(2)} {P(OH)Ph(2)}], where {S-S}(-) ={S(2)CNEt(2)}(-) (1), {S2P(OEt)2}(-) (2) and {S(2)COEt}(-) (3). Complexes 2 and 3 reacted with an excess of NaI in acetone solution by dealkylation of the coordinated dithiolate ligand and formation of the compounds [Pt{S2P(O) (OEt)} {P(O)Ph(2)} {P(OH)Ph(2)}] Na (4) and [Pt{S2CO}{P(O)Ph(2)}{P(OH)Ph(2)}] Na (5), respectively. The corresponding tetraphenylphosphonium derivatives (6, 7) were prepared by a metathetical reaction of these complexes with Ph(4)PBr in acetone solution. Related dithiolate complexes were obtained by reaction of the complex [Pt{S-S}(2)] with P(OMe)Ph(2) in molar ratio 1:2. Thus, the reaction of [Pt{S(2)COEt}(2)] in dichloromethane solution at room temperature gave [Pt{S(2)COEt} {P(OMe)Ph(2)}(2)] Cl (8). This complex reacted with NaI in acetone to form the neutral compound [Pt{S2CO} {P(OMe)Ph(2)}(2)] (9). When the reaction was carried out in dichloromethane at reflux temperature using [Pt{S2P(OEt)(2)}(2)] as starting material, the neutral compound [Pt{S2P(O)(OEt)} {P(OMe)Ph(2)}(2)] (10) was obtained. The crystal structure of the complex 9 has been determined by X-ray diffraction. The neutral complex shows a nearly square-planar coordination of the metal and a planar dithiocarbonate ligand.
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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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    Synthesis and characterization of heterodinuclear RuPt and IrPt complexes containing pyrazolate bridging ligands.: Crystal structure of [(η5-C5Me5)Ir(μ-pz)3PtMe3] (pz = pyrazolate)
    (2000) Contreras, R; Valderrama, M; Orellana, EM; Boys, D; Carmona, D; Oro, LA; Lamata, MP; Ferrer, J
    The reaction of the metallo-ligand [Ru(eta(6)-p-cymene)(pz)(2)(Hpz)] with the platinum complex [{PtIMe3}(4)] affords mixtures of the heterodinuclear complexes [(eta(6)-p-cymene)Ru(mu-pz)(3)PtMe3] (1) and [(eta(6)-p-cymene)Ru(mu-pz)(2)(mu-I)PtMe3] (2). The reaction of the iridium derivative [Ir(eta(5)-C5Me5)(pz)(2)(Hpz)] with [{PtIMe3}(4)] gives [(eta(5)-C5Me5)Ir(mu-pz)(2)(mu-I)PtMe3] (3). Both [Ru(eta(6)-p-cymene)(pz)(2)(Hpz)] and [Ir(eta(5)-C5Me5)(pz)(2)(Hpz)] react with [{PtIMe3}(4)] in the presence of NaOH yielding 1 and [(eta(5)-C5Me5)Ir(eta-pz)(3)PtMe3] (4), respectively. While [Ru(eta(6)-p-cymene)(pz)(2)(Hpz)] reacts with [PtBr2Me2Sx] to give mixtures of [(eta(6)-p-cymene)Ru(mu-pz)(3)PtBrMe2] (5) and [(eta(6)-p-cymene)Ru(mu-pz)(2)(mu-Br)PtBrMe2] (6), the reaction of [Ir(eta(5)-C5Me5)(pz)(2)(Hpz)] with [PtBr2Me2Sx] gives [(eta(5)-C5Me5)Ir(mu-pz)(2)(mu-Br)PtBrMe2] (7) as the sole product. All species were characterized in solution by H-1-NMR spectroscopy. The crystal structure of complex 4 has been determined by single-crystal X-ray diffraction. (C) 2000 Elsevier Science S.A. All rights reserved.
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    Synthesis and characterization of new dimethylplatinum(IV) complexes with O-(diphenylphosphino)thioanisole and its chalcogenide derivatives as ligands.: Crystal structure of trans-[Me2PtBr2{O-Ph2P(S)C6H4SMe-S,S'}]
    (2001) Contreras, R; Valderrama, M; Beroggi, C; Boys, D
    The compound o-(diphenylphosphino)thioanisole can be oxidized by S or Se in benzene leading to the derivatives Ph2P(E)C6H4SMe [EPSMe: E = S (1), Se (2)]. These compounds act as bidentate chelate ligands in reactions with the platinum(IV) complex [Me2PtBr2](n) to form trans and cis isomers of the general formula [Me2PtBr2(L-2)] [L-2 = SPSMe (3, 4); SePSMe (5, 6)]. The reaction of the complex [Me2PtBr2](n) with the starting ligand Ph2PC6H4SMe (PSMe) led to a reductive elimination affording the neutral complex [PtBr2(PSMe)] (7). The structure of the complex [Me2PtBr2{o-Ph2P(S)C6H4SMe}] was established by X-ray crystallography. The platinum atom has a distorted octahedral coordination and it is bonded to two methyl carbons, two bromide atoms and two sulfur atoms of the (o-diphenylphosphinesulfide)thioanisole bidentate ligand. (C) 2001 Elsevier Science Ltd. Ail rights reserved.
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    Synthesis and characterization of new homo-heterobinuclear platinum(II) complexes with dimethylphosphonate as bridging ligands. Crystal structure of [(eta(2)dppm)Pt{mu-P(O)(OMe)(2)}(2)(mu-I)PtMe(3)]
    (1997) Contreras, R; Valderrama, M; Nettle, A; Boys, D
    The preparation of the new neutral complex [(eta(2)-dppm)Pt{P(O)(OMe)(2)}(2)] (1) (dppm = 1,1-bis(diphenylphosphino) methane) and its behaviour as a chelate (O,O)-donor ligand is described. This ligand reacts with [Me(3)PtI](4) to give the homobimetallic complex [(eta(2)dppm)Pt{mu-P(O)(OMe)(2)}(2)(mu-I)PtMe(3)] (2), which in turn reacts with AgPF6 in the presence of PPh(3) to yield the new cationic complex [(eta(2)dppm)Pt{mu-P(O)(OMe)(2)}(2){PtMe(3)(PPh(3))}]PF6 (3). In contrast, the treatment of binuclear complexes [{Pd(mu-Cl)(2-MeC(3)H(4))}(2)] and [{Rh(mu-Cl)(cod)}(2)] with silver perchlorate in the presence of the bidentate ligand 1 yields the heterobinuclear compounds [(eta(2)dppm)Pt{mu-P(O)(OMe)(2)}Pd-2(eta(3)MeC(3)H(4))]ClO4 (4) and [(eta(2)dppm)Pt{mu-P(O)(OMe)(2)}Rh-2(cod)]ClO4 (5). Complex 5 reacts with an atmosphere of CO at room temperature yielding the cis-dicarbonyl complex [(eta(2)dppm)Pt{mu-P(O)(OMe)(2)}Rh-2(CO)(2)]ClO4 (6). The structure of complex [(eta(2)dppm)Pt{mu-P(O)(OMe)(2)}(2)(mu-I)PtMe(3)] has been determined by single crystal X-ray diffraction methods.
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    Synthesis and reactivity of new trimethylplatinum(IV) complexes containing chiral Schiff bases as ligands: Crystal structure of (OC-6-44-C)-[PtIMe3{kappa(2)-(R)-Ph2P(C6H4)CH=NC*H(Ph)Me-P,N}]
    (ELSEVIER SCIENCE SA, 2006) Ramirez, P; Contreras, R; Valderrama, M; Boys, D
    Reaction of the tetranuclear complex [PtIMe3](4) with the ligand (S)- and (R)-Ph2P(C6H4)CH=NC*H(Ph)Me in a 1:4 molar ratio yields the mononuclear neutral complexes in diastereoisomeric mixtures [PtIMe3{K-2-Ph2P(C6H4)CH=NC*H(Ph)Me-P,N}]. Iodide abstraction from mixture with AgBF4 in the presence of pyridine (Py) induces a reductive elimination reaction with loss of ethane, leading to the cationic complex [PtMe(Py) {kappa(2) -Ph2P(C6H4)CH=NC*H(Ph)Me-P,N}[BF4] [C* = (S)-, 3; (R)-, 4]. When this reaction was carried out in the presence of PPh3 a consecutive orthometallation reaction with loss of methane is produced, forming the cationic complex [Pt(PPh3){kappa(3)-Ph2P(C6H4)CH=NC*H(C6H4)Me-C,P,N][BF4], [(S)-, 5; (R)-, 6]. All species were characterised in solution by H-1 and P-31{H-1} NMR spectroscopy, elemental analysis and mass spectrometry.
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    Synthesis and single-crystal characterization of the square planar complex [Ni{(SPPh2)2 N-S,S′}2]•2THF
    (2001) Simón-Manso, E; Valderrama, M; Boys, D
    Reaction of Ni(CO)(4) with HN(SPPh2)(2) in tetrahydrofuran yielded the nickel(II) neutral complex [Ni-{(SPPh2)(2)}(2)N-S,S'].2THF. X-ray crystallography shows a square planar NiS4 core, with a center of inversion at Ni atom. It crystallized in the space group P(1)over-bar. This compound easily isomerizes in organic solvents at room temperature or by heating a solid-state sample to form the corresponding tetrahedral isomer.
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    Synthesis of rhodium(III) complexes with the chiral phosphine (S)-Ph2PCH2CHMeCH2OH.: Crystal structure of (SRhSC)-[(η5-C5Me5)RhCl(η2-PPh2CH2CHMeCH2OH-P,O)]BF4
    (2001) Valderrama, M; Contreras, R; Araos, G; Boys, D
    Reaction of dinuclear complex [{(eta (5)-C5Me5)RhCl}(2)(mu -Cl)(2)] with the chiral phosphine (S)-Ph2PCH2CHMeCH2OH leads to the complex [{eta (3)-C5Me5)RhCl2(eta (1)-PPh2CH2CHMeCH2OH-P)] (1). Complex 1 reacts with NaH and T1BF(4) affording the chiral-at-metal rhodium compounds [(eta (5)-C5Me5)RhCl(eta (2)-PPh2CH2CHMeCH2O-P,O)] (2) and [(eta (5)-C5Me5)RhCl(eta (2)-PPh2CH2CHMeCH2OH-P,O)]BF4(3), respectively. Complex 2 has been alternatively prepared by reaction of [{(eta (5)-C5Me5)RhCl}(2)(mu -Cl)(2)] with the sodium salt Ph2PCH2CHMeCH2ONa. Complex 2 reacts with HBF, to give 3. The reaction of 3 with an excess of NaI affords the neutral complex [(eta (5)-C5Me5)RhI2(eta (1)-PPh2CH2CHMeCH2OH-P)] (4). All the complexes have been characterised by elemental analyses and multinuclear NMR spectroscopy. The crystal structure of complex 3 has been determined by X-ray diffraction. (C) 2001 Elsevier Science B.V. All rights reserved.
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    Synthesis, crystal structure, molecular orbital calculations and electronic properties of 2,3-di(2-pyridyl)naphtho[2,3-f]quinoxaline-7,12-quinone (Aqdpp)
    (ROYAL SOC CHEMISTRY, 1998) Lopez, R; Boys, D; Loeb, B; Zuloaga, F
    The synthesis, characterization and crystal structure of 2,3-di(2-pyridyl)naphtho[2,3-f]quinoxaline-7,12-quinone (Aqdpp) are reported. Molecular orbital calculations have been carried out in order to characterize its reactivity and coordination properties. surface maps for the electronegativity, hardness and Fukui functions have been generated to identify local reactivity sites and the crystal structure has been compared with the optimized geometry with good correlation among them. The acceptor properties of the Aqdpp ligand are shown by the orbital map for the LUMO level contributed mainly by the quinonic region of the ligand.
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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.