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PPh3
Terms modified by PPh3 Selected AbstractsProtein phosphatase 2A on track for nutrient-induced signalling in yeastMOLECULAR MICROBIOLOGY, Issue 4 2002Piotr Zabrocki Summary Early studies identified two bona fide protein phosphatase 2A (PP2A)-encoding genes in Saccharo-myces cerevisiae, designated PPH21 and PPH22. In addition, three PP2A-related phosphatases, encoded by PPH3, SIT4 and PPG1, have been identified. All share as much as 86% sequence similarity at the amino acid level. This review will focus primarily on Pph21 and Pph22, but some aspects of Sit4 regulation will also be discussed. Whereas a role for PP2A in yeast morphology and cell cycle has been readily recognized, uncovering its function in yeast signal transduction is a more recent breakthrough. Via their interaction with phosphorylated Tap42, PP2A and Sit4 play a pivotal role in target of rapamycin (TOR) signalling. PPH22 overexpression mimics overactive cAMP,PKA (protein kinase A) signalling and PP2A and Sit4 might represent ceramide signalling targets. The methylation of its catalytic subunit stabilizes the heterotrimeric form of PP2A and might counteract TOR signalling. We will show how these new elements could lead us to understand the role and regulation of PP2A in nutrient-induced signalling in baker's yeast. [source] [FeFe]-Hydrogenase Models: Overpotential Control for Electrocatalytic H2 Production by Tuning of the Ligand ,-Acceptor AbilityEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 25 2010Fengwei Huo Abstract In the search for synthetic competitive catalysts that function with hydrogenase-like capability, a series of (Pyrrol-1-yl)phosphane-substituted diiron complexes [(,-pdt)Fe2(CO)5L] [pdt = propanedithiolate, L = Ph2PPyr (2), PPyr3 (4); Pyr = pyrrolyl] and [(,-pdt)Fe2(CO)4L2] [L = Ph2PPyr (3), PPyr3 (5)] were prepared as functional models for the active site of Fe-only hydrogenase. The structures of these complexes were fully characterized by spectroscopy and X-ray crystallography. In the IR spectra the CO bands for complexes 2,5 are shifted to higher energy relative to those of complexes with "traditional" phosphane ligands, such as PPh3, PMe3, and PTA (1,3,5-triaza-7-phosphaadamantane), indicating that (pyrrol-1-yl)phosphanes are poor ,-donors and better ,-acceptors. The electrochemical properties of complexes 2,5 were studied by cyclic voltammetry in CH3CN in the absence and presence of the the weak acid HOAc. The reduction potentials of these complexes show an anodic shift relative to other phosphane-substituted derivatives. All of the complexes can catalyze proton reduction from HOAc to H2 in CH3CN at their respective FeIFe0 level. Complex 4 is the most effective electrocatalyst, which catalytically generates H2 from HOAc at ,1.66 V vs. Fc+/Fc with only ca. 0.2 V overpotential in CH3CN. [source] A Dinuclear Double-Stranded Oxido Complex of ReV with a Bis(benzene- o -dithiolato) LigandEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 27 2009Jorge S. Gancheff Abstract The reaction of [ReOCl3(PPh3)2] with 1,2-bis(2,3-dimercaptobenzamido)ethane (H4 - 1) in the presence of Na2CO3 in methanol under anaerobic conditions affords the dinuclear ReV oxido complex [PPh4]2[ReO(1)]2 containing two distorted square-pyramidal {ReVOS4} units bridged by the ligand strands in a double-stranded fashion. The coordinationgeometry around the metal centers is similar to the one observed for [ReO(bdt)2],. The ReS4 planes are arranged in a coplanar fashion and are not twisted around the metal,metal vector, which prevents the complex to adopt a helical structure. Luminescence studies show the presence of emission bands, which are assigned to singlet-singlet transitions exhibiting very fast decays (ca. 10 ns). Theoretical Density Functional (DFT) studies on geometry and electronic properties were performed employing the hybrid B3LYP and PBE1PBE functionals. While the general trends observed in the experimental data are well reproduced in all cases, a good agreement was obtained using PBE1PBE, in particular for the Re,S bonds. Natural Bond Orbitals (NBO) analysis indicates the presence of polarized Re,O and Re,S bonds, both of them polarized toward the non-metal. The calculation show that the molecular orbitals of the ReV are doubly degenerated, the occupied 5d orbital of rhenium lying beneath occupied sulfur-based MOs due to the rigid geometry imposed by the C,C backbone of the bis(benzene- o -dithiolato) ligands. The origin of all absorption bands is ascribed to a ligand-to-metal charge transfer (LMCT), in which occupied sulfur-based orbitals and unoccupied rhenium-centered orbitals are involved.(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009) [source] Copper Complexes with Neutral N4 Tripodal Ligands: Influence of the Number of Nitrogen Donors on Their Structures, Properties, and Reactivity,EUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 26 2009Kiyoshi Fujisawa Abstract Copper coordination complexes of the neutral tetradentate nitrogen-containing ligands tris(3,5-dimethylpyrazol-1-ylmethyl)amine (L0N4) and tris(3,5-diisopropylpyrazol-1-ylmethyl)amine (L1N4), namely the copper(II) chlorido complexes [CuII(L0N4)Cl2] (1) and [CuII(L1N4)Cl2] (2), the copper(II) nitrato complexes [CuII(L0N4)(NO3)](NO3) (3) and [CuII(L1N4)(NO3)](NO3) (4), and the copper(II) sulfato complexes [CuII(L0N4)(SO4)] (5) and [CuII(L1N4)(SO4)] (6), and the copper(I) complexes [CuI(L0N4)](PF6) (7) and [CuI(L0N4)(PPh3)](ClO4) (8), have been systematically synthesized in order to investigate the influence of the number of nitrogen donors on their structures, properties, and reactivity. All copper(II) complexes were fully characterized by X-ray crystallography and by IR/far-IR, UV/Vis absorption, and ESR spectroscopy. Although the structure of 7 was not determined by X-ray crystallography, this complex and the structurally characterized copper(I) triphenylphosphane complex 8 were fully characterized by IR/far-IR and NMR spectroscopy. A comparison of the copper(II) complexes with two tris(pyrazol-1-ylmethyl)amine ligands with different bulkiness of the pyrazolyl rings has allowed us to evaluate the second coordination sphere effects of the ligands. Moreover, the structures and physicochemical properties of these complexes are compared with those of related complexes containing the neutral tridentate tris(pyrazolyl)methane ligand and the neutral bidentate bis(pyrazolyl)methane ligand. Finally, the relative stability of the copper(I) complexes is discussed. The influence of the number of nitrogen donors in copper complexes is observed from these systematic results.(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009) [source] Cyanoimide-Bridged, Bi- and Trinuclear, Heterometallic Complexes with an NCN,Mo,NCN Phosphinic CoreEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 26 2009Sónia M. P. R. M. Cunha Abstract The heterometallic dinuclear complexes of the types trans -[Mo(NCN)(dppe)2(,-NCN)M] [M = WCl4(PPh3), ReOCl3(PPh3) or mer -ReCl(N2)(PMePh2)3; dppe = Ph2PCH2CH2PPh2] and [Mo(NCN)(dppe)2(,-NCN)M][BF4]Br [M = trans -Fe(NCC6H4NO2 -4)(depe)2; depe = Et2PCH2CH2PEt2] and the trinuclear ones [Mo(dppe)2{(,-NCN)M}2] [M = VCl3(thf) or PtCl2(PEt3)] were prepared by reaction of the bis(cyanoimido)molybdenum complex trans -[Mo(NCN)2(dppe)2] with the corresponding transition-metal Lewis acid (M) precursors, particularly [VCl3(thf)3], [WCl4(PPh3)2], [ReOCl3(PPh3)2], trans -[ReCl(N2)(PMePh2)4], trans -[FeBr(NCC6H4NO2 -4)(depe)2][BF4] and [Pt2Cl4(PEt3)2]. These adducts were characterized by FTIR, 1H, 13C and 31P{1H} NMR spectroscopy, mass spectrometry and cyclic voltammetry. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009) [source] Synthesis, Structure, Conductivity, and Calculated Nonlinear Optical Properties of Two Novel Bis(triphenylphosphane)copper(I) Dithiocarbamates,EUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 18 2009Abhinav Kumar Abstract A centrosymmetric binuclear [{Cu(PPh3)2}2(piperzdtc)] (1) [piperzdtc2, = piperazinebis(dithiocarbamate)] and another mononuclear [{Cu(PPh3)2}(BzMedtc)] (2) (BzMedtc, = N -benzyl- N -methyldithiocarbamate) complex have been synthesized and characterized by elemental analyses, IR, 1H, 13C, and 31P NMR spectroscopy and by X-ray crystallography. The nonlinear optical properties of 2 have been investigated by density functional theory and its electronic absorption bands have been assigned by time-dependent density functional theory (TD-DFT). Both complexes are weakly conducting (,rt , 10,8 S,cm,1) because of the absence of M···S/S···S intermolecular stacking and exhibit semiconductivity with band gaps of 0.94 and 1.24 eV, respectively.(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009) [source] Synthesis and Reactivity of Ru(NHC)(dppp)(CO)H2 and Ru(NHC)(dppp)(CO)HF Complexes: C,H and C,F ActivationEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 13 2009Steven P. Reade Abstract The hydrido fluorido ruthenium(II) complex [Ru(PPh3)(dppp)(CO)HF] [1, dppp = 1,4-bis(diphenylphosphanyl)propane], which forms upon reaction of [Ru(PPh3)3(CO)HF] with dppp, reacts with IMes [1,3-bis(2,4,6-trimethylphenyl)imidazol-2-ylidene] to give the expected carbene-containing hydrido fluorido complex [Ru(IMes)(dppp)(CO)HF] (2), as well as the C,H activated species [Ru(IMes),(dppp)(CO)H] (3). The formation of the latter product results from the reaction of 2 with a base (IMes or Et3N). Displacement of PPh3 from [Ru(PPh3)(dppp)(CO)H2] by ICy (1,3-dicyclohexylimidazol-2-ylidene) yields [Ru(ICy)(dppp)(CO)H2] (7), which upon reaction with Et3N·3HF, gives [Ru(ICy)(dppp)(CO)HF] (8). Thermolysis of 7 with C6F6 at elevated temperature generates 8 and [Ru(ICy)(dppp)(CO)(C6F5)H] (9). The related fluoroaryl complexes [Ru(ICy)(dppp)(CO)(C6F4CF3)H] (10) and [Ru(ICy)(dppp)(CO)(C5F4N)H] (11) are formed upon the room temperature C,F activation of C6F5CF3 and C5F5N by 7, but also by C,H activation of the partially fluorinated substrates p -C6F4HCF3 and p -C5F4HN.(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009) [source] The Role of Axial Ligation in Nitrate Reductase: A Model Study by DFT Calculations on the Mechanism of Nitrate ReductionEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 34 2008Kuntal Pal Abstract The reactivity differences of the model anionic complexes [Mo(mnt)2(X)(PPh3)], [mnt2, = 1,2-dicyanoethylenedithiolate; X = SPh (1a), SEt (1b), Cl (1c), Br (1b)] towards oxygen atom transfer from nitrate, which is a key step performed by nitrate reductase, has been investigated by density functional theory calculations. Unlike complexes 1a and 1b, complexes 1c and 1d do not react with nitrate. Thermodynamically, all these complexes have a similar ability to generate the pentacoordinate active state [Mo(mnt)2(X)], by dissociation of PPh3, although the inaccessibility of the dxy orbital in 1c,d and the instability of the corresponding nitrate-bound enzyme substrate (ES) type complex contributes to their failure to reduce nitrate. The nature of the ES complex for 1a,b is described. The variation in the experimental data due to the change of axial ligation from SPh to SEt on the catalytic pathway has also been addressed. The gas-phase and solvent-corrected potential energy surface for the reaction of 1a,b with nitrate are established with fully optimized minima and transition states.(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008) [source] Preparation, Geometric and Electronic Structures of [Bi2Cu4(SPh)8(PPh3)4] with a Bi2 Dumbbell, [Bi4Ag3(SePh)6Cl3(PPh3)3]2 and [Bi4Ag3(SePh)6X3(PPhiPr2)3]2 (X = Cl, Br) with a Bi4 UnitEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 32 2008Heino Sommer Abstract BiBr3 and CuCl react with S(Ph)SiMe3 in thf solution in the presence of PPh3 to yield [BiCu2(SPh)3Br2(PPh3)3] (1). The reaction of 1 with 2 equiv. of NaSPh gives rise to [Bi2Cu4(SPh)8(PPh3)4] (2) containing a Bi2 dumbbell. In this paper we further report the synthesis and characterization of the new cluster complexes [Bi4Ag3(SePh)6Cl3(PPh3)3]2 (3) and[Bi4Ag3(SePh)6X3(PPhiPr2)3]2 [X = Cl (4), Br (5)]. In the surprisingly formed species 3,5 a formal charged Bi46+ unit is observed. Compounds 3,5 were prepared by the reaction of BiX3 (X = Cl, Br), AgStBu, Se(Ph)SiMe3 and phosphane (PPh3, PPhiPr2). The structures of the compounds were determined by single-crystal X-ray analysis. Additionally, theoretical investigations were preformed to rationalize the bonding situation in 2,5. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008) [source] Variable Coordination Modes of Benzaldehyde Thiosemicarbazones , Synthesis, Structure, and Electrochemical Properties of Some Ruthenium ComplexesEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 29 2008Swati Dutta Abstract Reaction of benzaldehyde thiosemicarbazones [H2LR, where H2 stands for the two protons, the hydrazinic proton, and the phenyl proton at the ortho position, with respect to the imine function and R (R = OCH3, CH3, H, Cl, and NO2) for the para substituent] with [Ru(PPh3)2(CO)2Cl2], carried out in refluxing ethanol, afforded monomeric complexes of type [Ru(PPh3)2(CO)(HLR)(H)]. The crystal structure of the [Ru(PPh3)2(CO)(HLNO2)(H)] complex was determined. The thiosemicarbazone ligand is coordinated to the ruthenium center as a bidentate N,S-donor ligand forming a four-membered chelate ring. When the reaction of the thiosemicarbazones with [Ru(PPh3)2(CO)2Cl2] was carried out in refluxing toluene, a family of dimeric complexes of type [Ru2(PPh3)2(CO)2(LR)2] were obtained. The crystal structure of [Ru2(PPh3)2(CO)2(LCl)2] was determined. Each thiosemicarbazone ligand is coordinated to one ruthenium atom, by dissociation of the two protons, as a dianionic tridentate C,N,S-donor ligand, and at the same time the sulfur atom is also bonded to the second ruthenium center. 1H NMR spectra of the complexes of both types are in excellent agreement with their compositions. All the dimeric and monomeric complexes are diamagnetic (low-spin d6, S = 0) and show intense absorptions in the visible and ultraviolet regions. Cyclic voltammetry of the [Ru(PPh3)2(CO)(HLR)(H)] and [Ru2(PPh3)2(CO)2(LR)2] complexes show the ruthenium(II),ruthenium(III) oxidation within 0.48,0.73 V vs. SCE followed by a ruthenium(III),ruthenium(IV) oxidation within 1.09,1.47 V vs. SCE. Potentials of both the oxidations are found to correlate linearly with the electron-withdrawing character of the substituent R. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008) [source] Nickel Complexes and Cobalt Coordination Polymers with Organochalcogen (S, Se) Ligands Bearing an N -Methylimidazole Moiety: Syntheses, Structures, and Properties,EUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 26 2008Wei-Guo Jia Abstract The organochalcogen ligands (S, Se) derived from 3-methylimidazole-2-thione/selone groups mbit (2a), mbis (2b), ebit (2c), and ebis (2d) [mbit = 1,1,-methylenebis(1,3-dihydro-3-methyl-2H -imidazole-2-thione), mbis = 1,1,-methylenebis(1,3-dihydro-3-methyl-2H -imidazole-2-selone), ebit = 1,1,-(1,2-ethanediyl)bis(1,3-dihydro-3-methyl-1H -imidazole-2-thione), ebis = 1,1,-(1,2-ethanediyl)bis(1,3-dihydro-3-methyl-1H -imidazole-2-selone)] were synthesized and characterized. Mononuclear NiII complexes NiBr2mbit (3a), NiBr2mbis (3b), NiBr2ebit (3c), and NiBr2ebis (3d) were obtained by the reactions of Ni(PPh3)2Br2 with 2a, 2b, 2c, and 2d, respectively. However, when the corresponding ligands 2a, 2b, 2c, and 2d were treated with CoCl2 in thf solution CoII 1D coordination polymers (CoCl2mbit)n (4a), (CoCl2mbis)n (4b), (CoCl2ebit)n (4c), and (CoCl2ebis)n (4d) were obtained. All compounds were fully characterized by IR spectroscopy and elemental analysis. The crystal structures of 2c, 3a, 3b, 3c, 4a, 4b, and 4c were determined by X-ray crystallography. The local geometry around the nickel atom in complexes 3a,c was distorted tetrahedron with coordinated S(Se) and two Br atoms, and the organochalcogen ligands form an eight- or a nine-membered ring with the nickel atom included. The cobalt atom coordination polymers 4a and 4b coexist as left-handed and right-handed helical chains, but 4c formed a zigzag chain with a CH3CN solvent molecule taken up in the channel structure. After activation with methylaluminoxane (MAO), the nickel complexes exhibited high activities for addition polymerization of norbornene (1.42,×,108 g,PNBmol,1,Nih,1 for 3a). The effects of the Al/Ni ratio, reaction temperature, and reaction time to norbornene polymerization were also investigated.(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008) [source] Study of the Effect of the Phosphane Bridging Chain Nature on the Structural and Photophysical Properties of a Series of Gold(I) Ethynylpyridine ComplexesEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 18 2008Montserrat Ferrer Abstract Alkynyl AuI complexes of the type [Au(C,CC5H4N)(PPh3)] (1) [Au2(C,CC5H4N)2 (diphosphane)] [diphosphane = bis(diphenylphosphanyl)methane (2), bis(diphenylphosphanyl)isopropane] (3), bis(diphenylphosphanyl)acetylene (4), 1,2-bis(diphenylphosphanyl)ethane (5), 1,3-bis(diphenylphosphanyl)propane (6), 1,4-bis(diphenylphosphanyl)butane (7), 1,1,-bis(diphenylphosphanyl)ferrocene (8) and [Au3(C,CC5H4N)3(triphos)] [triphos = 1,1,1-tris(diphenylphosphanylmethyl)ethane] (9) were prepared by reaction of [Au(C,CC5H4N)]n with the suitable phosphane. Determination of the X-ray crystal structures of several compounds bearing different carbon backbones between the phosphorus atoms reveals the influence of the nature of the phosphane spacer on the establishment of intra and/or intermolecular gold,gold interactions. The absorption and emission properties of the complexes were analysed by taking into account the presence or absence of intermetallic interactions. Although UV/Vis spectra show differences for compounds with intramolecular Au,Au contacts, a conclusive trend was not observed in the emission behaviour. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008) [source] Electron-Sponge Behavior, Reactivity and Electronic Structures of Cobalt-Centered Cubic Co9Te6(CO)8 ClustersEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 12 2008Mustapha Bencharif Abstract Extended investigations of the reaction sequence [Cp,2Nb(Te2)H]/CH3Li/[Co2(CO)8] (Cp, = tBuC5H4) led to the identification of Lin[3] {3 = [Co9Te6(CO)8]; n = 1, 2} salts through their transformation with [PPN]Cl into [PPN]n[3] (PPN = Ph3PNPPh3). These compounds form in the solid state columnar ([PPN][3]) or undulated 2D ([PPN]2[3]) supramolecular networks. Electrochemical studies of [Cp*2Nb(CO)2][3] (Cp* = C5Me5) or [Na(THF)6][3] revealed the presence of the redox couples [3],/[3]2,/[3]3,/[3]4,/[3]5, regardless of the nature of the cation, whereas in the anodic part oxidative degradation of the cluster takes place. This behavior is in agreement with the observation that [3], containing salts form with PPh3AuCl or dppe decomposition products like [(PPh3)2Au][CoCl3PPh3] or [Co(CO)2dppe]2(,-Te). A neutral cluster comprising the Co@Co8(,4 -Te)6 core formed in the reaction of [Cp*2Nb(CO)2][Co11Te7(CO)10] with PPh3AuCl, which gave [Co9Te6(CO)4(PPh3)4] (4) after oxidative cluster degradation and CO substitution. 4 was characterized by X-ray crystallography. DFT calculations carried out on all members of the [3]n (n = +1 to ,5) family and on related species indicate that there is no significant Jahn,Teller distortion (and therefore no connectivity change) for any of the considered electron counts. Magnetic investigations on [PPN][3] show that the ground state of [3], is a spin triplet with spins interacting antiferromagnetically in a 1D space.(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008) [source] New Heterodimetallic Platinum(II) Complexes Potentially Useful as Molecular SwitchesEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 10 2008Sonia Pérez Abstract Four types of platinum(II) complexes of general formulae [Pt(FcCH=NC6H4OH-2)Cl2(L)] [Fc = (,5 -C5H5)Fe(,5 -C5H4), L = dmso (2) or PhCN (3)], [Pt(FcCH=NC6H4O-2)Cl(dmso)] (4), [Pt{(,5 -C5H3CH=NC6H4O-2)Fe(,5 -C5H5)}(L)] [L = dmso (5) or PPh3 (6)] or [Pt{(,5 -C5H3CH=NC6H4OH-2)Fe(,5 -C5H5)}Cl(L)] [L = dmso (7) or PPh3 (8)] have been prepared. These compounds differ in the mode of binding of the ligand: (N) (in 2 and 3), (N,O), (in 4), [C(sp2, ferrocene),N,O]2, (in 5 and 6) or [C(sp2, ferrocene),N], (in 7 and 8). NMR, UV/Vis and electrochemical studies of 2 and 4,8 reveal that these products can be grouped in three pairs [(2c, 4b), (5, 7) and (6, 8)], and one of the compounds of each pair can be easily converted into its partner by a H+/OH, chemical input. The results obtained revealed that these transformations, that affect the spectroscopic and electrochemical properties, are reversible and robust. A study of the relevancy of the mode of binding of compounds 2 and 4,8 upon their potential utility of the new platinum(II) complexes as molecular switches is reported. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008) [source] Reductive Activation of tripod Metal Compounds: Identification of Intermediates and Preparative Application,EUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 9 2008Jürgen Mautz Abstract [tripodCoCl2] {tripod = CH3C(CH2PPh2)3} when treated with KC8 in THF solution under an argon atmosphere produces a reactive species ["tripodCo0"] (A) which undergoes oxidative additions with stannanes, [tripodCo(H)2(SnBu3)] (4), formed, for example, by addition of Bu3SnH. Silanes, R3SiH, undergo the same type of reaction producing [tripodCo(H)2(SiR3)] (R = Et: 5a; R = Ph: 5b). The solid-state structures of all the compounds [tripodCo(H)2(ER3)] (E = Si, R = Ph; E = Sn, R = Ph, Bu) are rather similar. While they contain six-coordinate cobalt with the formal oxidation state of cobalt being +III the coordination geometry is not octahedral: the heteroelement E deviates from the position which it would have in octahedral coordination by around 40° while the other five ligands, three phosphorus and two hydrogen, have the expected interligand angles of around 90° and 180°, respectively. The deviation of the heteroelement E is such that it approaches the metal bonded hydrogen atoms leading to short H···E contacts of only about 190 pm (E = Si) and 230 pm (E = Sn), respectively. The generation of a reactive species ["tripodCo0"] (A) was transferred to the synthesis of a reactive tripodnickel(0) species by treating a THF solution of [(DME)NiBr2] with KC8 in the presence of tripod. This species reacts with two electron donor ligands L to produce the pseudo tetrahedral compounds [tripodNi(L)] {L = PPh3 (6), AsPh3 (7), cHexNC (8), tBuNC (9), C2H4 (10)}. The identity of the reactive nickel(0) species as unequivocally deduced from NMR experiments is [tripod4Ni3] (12). All compounds were characterised by the usual analytic techniques including X-ray analysis where applicable.(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008) [source] Indenylidene-Ruthenium Complexes Bearing Saturated N-Heterocyclic Carbenes: Synthesis and Catalytic Investigation in Olefin Metathesis ReactionsEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 3 2008Stijn Monsaert Abstract The synthesis of complexes of the general formula Cl2Ru(SIMes)(L)(3-phenylinden-1-ylidene) (5, L = PCy3; 6, L = py; and 7, L = PPh3) from Cl2Ru(PR3)2(3-phenylinden-1-ylidene) (2a, R = Ph; 2b, R = Cy) is reported. This family of olefin metathesis catalysts was fully characterized (1H, 13C and 31P NMR spectroscopy and elemental analysis) and provided excellent activity in the ring-opening metathesis polymerization of 1,5-cyclooctadiene and the ring-closing metathesis of diethyl diallylmalonate. Comparison with the corresponding benzylidene-containing catalysts, 1a,c and 8b, established the decisive role of the carbene ligand on the procedure of the reaction and led to the observation of an unusual catalytic phenomenon, here called "self-inhibition".(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008) [source] Benzylideneruthenium Complexes Bearing Pyridine-Based Ligands and Their Influence on the Formation of Mono- or Bis(pyridine) ComplexesEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 34 2007Wen-Zhen Zhang Abstract Benzylideneruthenium complexes bearing the N-heterocyclic carbene (NHC) ligand 1,3-bis(2,6-dimethylphenyl)-4,5-dihydroimidazol-2-ylidene (H2IMe) and one or two pyridine-based ligands have been prepared by treating [RuCl2(=CHPh)(H2IMe)(PPh3)] with the corresponding pyridine derivative. X-ray crystallographic and mass spectrometric evidence is used to investigate the interconversion between mono- and bis(pyridine) complexes and the influence of the pyridine ligand on the formation of these complexes. The catalytic activity of these complexes has been tested in the ring-closing metathesis (RCM) reaction of diallylmalononitrile and the cross metathesis (CM) reaction of acrylonitrile with terminal olefins.(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007) [source] Cyanometalate Cages with Exchangeable Terminal LigandsEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 18 2007Julie L. Boyer Abstract The coordination chemistry of the unusual metallo-ligand Cs,[CpCo(CN)3]4[Cp*Ru]3 (Cs,Co4Ru3) is described with attention to the behavior of the ligand itself, its binding to Lewis-acidic metal cations, and its ability to stabilize catalytically relevant Ru,PPh3 fragments. A series of tests demonstrate that the "rim" [CpCo(CN)3], groups in Cs,Co4Ru3 are exchangeable. Upon treatment with [(MeC5H4)Co(CN)3], (Co,) Cs,Co4Ru3 undergoes vertex exchange to give Cs,Co4,xCo,xRu3. Similarly the cage is degraded by CO. Most convincing, Cs,Co4Ru3 reacts with PhNH3OTf to precipitate the polymer PhNH3CpCo(CN)3 and form the molecular box [Cs,Co4Ru4]+. Treatment of Cs,Co4Ru3 with [M(NCMe)x]PF6 (M = Cu, Ag) gave the Lewis acidic cages {Cs,[CpCo(CN)3]4[Cp*Ru]3M(NCMe)}PF6, which reacted with tertiary phosphane ligands to give adducts [Cs,Co4Ru3M(PPh3)]PF6. Lewis acidic octahedral vertices were installed using Fe, Ni, and Ru reagents. The boxes [Cs,Co4Ru3M(NCMe)3]2+ (M = Ni, Fe) formed readily from the reaction Cs,Co4Ru3 with [Ni(NCMe)6](BF4)2 and [Fe(NCMe)6](PF6)2. Displacement of the MeCN ligands gives [Cs,Co4Ru3Ni(9-ane-S3)](BF4)2. A series of boxes were prepared by the reaction of Cs,Co4Ru3 and RuCl2(PPh3)3, RuHCl(PPh3)3, and [(C6H6)Ru(NCMe)3](PF6)2. The derivative of the hydride, [Cs,Co4Ru3Ru(NCMe)(PPh3)2](PF6)2, was characterized crystallographically.(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007) [source] A Trinuclear Aqua Cyano-Bridged Ruthenium Complex [{(,5 -C5H5)(PPh3)2Ru(,-CN)}2RuCl2(PPh3)(H2O)]PF6: Synthesis, Characterization and Crystal StructureEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 13 2007Viatcheslav Vertlib Abstract The organometallic trinuclear aqua cyano-bridged complex [{(,5 -C5H5)(PPh3)2Ru(,-CN)}2RuCl2(PPh3)(H2O)]PF6 (1), in which the fragment [RuCl2(PPh3)(H2O)] acts as a bridge and an acceptor group between the two terminal cyclopentadienyl ruthenium cyano moieties, was isolated in moderate yield from the reaction of [(,5 -C5H5)(PPh3)2RuCN] with [RuCl2(PPh3)3] in THF. To the best of our knowledge, compound 1 is one of the few examples of a trinuclear array of ruthenium fragments bridged by the nitrogen atom of the,C,N, group (Ru,C,N,Ru,,N,C,Ru) with a Ru-coordinated water molecule. The new aqua complex was structurally characterized by FTIR, 1H, 13C, and 31P NMR spectroscopy, mass spectrometry, elemental analysis, single-crystal X-ray diffraction, and cyclic voltammetry. The title complex crystallizes in a triclinic unit cell a = 17.3477(6) Å, b = 17.8551(5) Å, c = 18.2460(7) Å, , = 95.693(2)°, , = 111.648(2)°, and , = 97.839(2)° in the space group P with Z = 2.(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007) [source] N -(Aryl)picolinamide Complexes of Ruthenium: Usual Coordination and Strategic CyclometalationEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 9 2007Sumon Nag Abstract Reaction of five N -(4- R -phenyl)picolinamides (R = OCH3, CH3, H, Cl, and NO2) with [Ru(PPh3)2(CO)2Cl2] in refluxing 2-methoxyethanol in the presence of a base (NEt3) affords two geometrical isomers of a group of complexes (1-R and 2-R), each of which contains an amide ligand coordinated to the metal center as a monoanionic bidentate N,N donor along with two triphenylphosphanes, a carbonyl, and a hydride. Similar reaction of N -(naphthyl)picolinamide with [Ru(PPh3)2(CO)2Cl2] affords an organometallic complex, 3, in which the amide ligand is coordinated to the metal center, by C,H activation of the naphthyl ring at the 8-position, as a dianionic tridentate N,N,C donor along with two triphenylphosphanes and one carbonyl. Structures of the 1-OCH3, 2-CH3, and 3 complexes have been determined by X-ray crystallography. In all the complexes the two triphenylphosphanes are trans. In the 1-R complexes the hydride is trans to the pyridine nitrogen and in the 2-R complexes it is trans to the amide-nitrogen. All the complexes are diamagnetic, and show characteristic 1H NMR signals and intense MLCT transitions in the visible region. Cyclic voltammetry on all the complexes shows a RuII,RuIII oxidation within 0.71,0.93 V versus SCE. An oxidation and a reduction of the coordinated amide ligand are also observed within 1.29,1.69 V versus SCE and ,1.02 to ,1.21 V versus SCE respectively.(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007) [source] Synthesis, Structures, and Electronic Spectroscopy of Luminescent Acetylene- and (Buta-1,3-diyne)platinum ComplexesEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 3 2007Ke Zhang Abstract The electronic absorption and emission spectroscopy of a series of diphenylaceylene- and (buta-1,3-diyne)-Pt0 complexes (L)Pt[(1,2-,2)-R,(C,C)n,R] and [(dppp)Pt]2[,-(1,2-,2):(3,4-,2)-R,(C,C)2,R] {R = Ph or CH3, L = dppp or(PPh3)2, n = 1 or 2} was investigated. The structures of(dppp)Pt[(1,2-,2)-Ph,C,C,Ph], (dppp)Pt[(1,2-,2)-PhC4Ph] and [(dppp)Pt]2[,-(1,2-,2):(3,4-,2)-Ph,(C,C)2,Ph] were characterized by X-ray diffraction. The complexes all display intense absorptions that were attributed to Pt,P(d,*) and Pt,acetylene(,x*) transitions. Except for the CH3C4CH3 complexes, the complexes all exhibit two emissions at 380,550 nm and 500,800 nm. The higher energy emission could arise from the 3[P(d,*),Pt] transition, and the lower energy emission, which has a longer lifetime than the higher energy one, was attributed to the 3[acetylene(,x*),Pt] transition. The energy of the MLCT absorption and emission was affected by the electronic properties of the acetylenes and the ancillary phosphanes. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007) [source] Reactivity and X-ray Structural Studies in Ligand Substitution of [Cp/(Ind)Ru(dppf)Cl] , Epimerisation in [Cp/(Ind)Ru(Josiphos)Cl] {Cp = ,5 -C5H5, Ind = ,5 -C7H9, dppf = 1,1,-Bis(diphenylphosphanyl)ferrocene, Josiphos = (R)-(,)-1-[(S)-2-(Diphenylphosphanyl)ferrocenyl]ethyldicyclohexylphosphane}EUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 3 2007Sin Yee Ng Abstract Ligand substitution of [(Ind)Ru(PPh3)2Cl] (1) led to the isolation of [(Ind)Ru(PPh3){Ph2P(CH2)2C9H7}Cl] (2), [(Ind)Ru(dppf)Cl] (3) and [(Ind)Ru{(Ph2PCH2)3CMe}]PF6 ([4]PF6), and diastereoisomers [(R)- and (S)-(Ind)Ru(Josiphos)Cl] [(R)- 5 and (S)- 5], where (R)-(S)-Josiphos is the ferrocene-based chiral diphosphane ligand (R)-(,)-1-[(S)-2-(diphenylphosphanyl)ferrocenyl] ethyldicyclohexylphosphane. The Cp analogues of 5, viz. (R)- 6 and (S)- 6, were also obtained from [CpRu(PPh3)2Cl] (1a). Josiphos-dependent epimerisation was observed, with conversion of the (S) isomer to the (R) isomer in both cases. Chloride abstraction of 3 with NaPF6 in CH3CN and NaN3 in EtOH gave [(Ind)Ru(dppf)(CH3CN)]PF6 ([7]PF6) and [(Ind)Ru(dppf)(N3)] (8), respectively. The azido ligand in 8 underwent [3+2] dipolar cycloaddition with dimethyl acetylenedicarboxylate to give a N -bound bis(methoxycarbonyl)-1,2,3-triazolato complex, 9. X-ray crystal structures of the new complexes, except (R)- 5, (S)- 5 and (S)- 6, have been determined. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007) [source] Synthesis and Structure of [nPr3N(CH2)6NnPr3][CuFe3Br3(SePh)6], [Cu5Fe(SePh)7(PPh3)4] and [Cu4Fe3(SePh)10(PPh3)4],EUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 1 2007Andreas Eichhöfer Abstract CuBr and Fe(OOCCH3)2 react with PhSeSiMe3 in acetonitrile in the presence of the diammonium salt [nPr3N(CH2)6NnPr3]Br2 to yield ionic [nPr3N(CH2)6NnPr3][CuFe3Br3(SePh)6]. The neutral complexes [Cu5Fe(SePh)7(PPh3)4] and [Cu4Fe3(SePh)10(PPh3)4] were obtained by similar reactions of different stoichiometric mixtures of CuOOCCH3 and FeCl2 with PPh3 and PhSeSiMe3. The crystal structures of the compounds were determined by single-crystal X-ray analysis to give new structural types of molecular cluster compounds formed by copper, iron and selenium. Thermal treatment of [Cu5Fe(SePh)7(PPh3)4] and [Cu4Fe3(SePh)10(PPh3)4] resultsin the formation of mixtures of binary Cu2Se and ternaryCuFeSe2.(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007) [source] Synthesis, Structural Characterisation and Reactions of Some Vinylgold(I) Phosphane ComplexesEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 4 2006Fabian Mohr Abstract A series of vinylgold(I) complexes [Au(CR=CHR)L] (R = H, Me; L = PPh3, PPh2Me, PPhMe2) were prepared from the reaction of the Grignard reagents [MgBr(CR=CHR)] (R = H, Me) with the gold(I) phosphane complexes [AuCl(L)] (L = PPh3, PPh2Me, PPhMe2) at low temperature. The complexes were characterised by various spectroscopic techniques and, in the case of [Au(CMe=CHMe)(PPh3)], by a single-crystal X-ray structure determination. The gold,carbon bonds of these vinylgold(I) complexes are easily cleaved by acids and, in the presence of potassium permanganate, by species containing acidic protons. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006) [source] Copper Complexes with (2,7-Di- tert -butylfluoren-9-ylidene)methanedithiolate: Oxidatively Promoted Dithioate Condensation,EUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 1 2006José Vicente Abstract The reaction of [Cu(NCMe)4]PF6 with piperidinium 2,7-di- tert -butyl-9H -fluorene-9-carbodithioate (pipH)[S2C(tBu-Hfy)] (1; tBu-Hfy = 2,7-di- tert -butylfluoren-9-yl), affords [Cun{S2C(tBu-Hfy)}n] (2), which reacts with various P ligands to give [Cu{S2C(tBu-Hfy)}L2] [L = PPh3 (3a), PCy3 (3b), PiPr3 (3d); L2 = 1,1,-bis(diphenylphosphanyl)ferrocene (dppf, 3c), bis(diphenylphosphanyl)methane (dppm, 3e)]. Compounds 3a,c react with atmospheric oxygen and moisture in the presence of NEt3 to give the dinuclear complexes [Cu2{[SC=(tBu-fy)]2S}L2] [tBu-fy = 2,7-di- tert -butylfluoren-9-ylidene; L = PPh3 (4a), PCy3 (4b); L2 = dppf (4c)], which contain a new dithiolato ligand formally resulting from the condensation of two dithioato ligands with loss of a sulfide ion and two protons. Neutral CuI dithiolate complexes of the type [Cu4{S2C=(tBu-fy)}2L4] [S2C=(tBu-fy) = [2,7-di- tert -butylfluoren-9-ylidene)methanedithiolate; L = PPh3 (5a), P(C6H4OMe- p)3 (5b), PiPr3 (5d) or L2 = dppf (5c)] were obtained by treating 1 with [Cu(NCMe)4]PF6, the corresponding phosphane, and piperidine in a 1:2:2:1 molar ratio. The reaction of 1 with Cu(ClO4)2·6H2O and (Pr4N)OH in a 2:1:2 molar ratio gives the CuII complex (Pr4N)2[Cu{S2C=(tBu-fy)}2] [(Pr4N)26], which readily oxidizes to the CuIII complex Pr4N[Cu{S2C=(tBu-fy)}2] (Pr4N7) in the presence of atmospheric oxygen and moisture. The salt PPN7 [PPN+ =(Ph3P)2N+] was obtained from 1, CuCl2·2H2O, PPNCl, and piperidine in a 2:1:1:2 molar ratio under aerobic conditions. The crystal structures of 3a, 3c·CH2Cl2, 4a·4Me2CO, and 4c·CH2Cl2 have been determined by X-ray diffraction studies. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006) [source] Synthesis, Structure and Reactivity of Homo- and Heterobimetallic Complexes of the General Formula [Cp*Ru(,-Cl)3ML] [LM = (arene)Ru, Cp*Rh, Cp*Ir]EUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 1 2006Laurent Quebatte Abstract The homo- and heterobimetallic complexes [Cp*Ru(,-Cl)3ML] [LM = (C6H6)Ru, (cymene)Ru, (1,3,5-C6H3iPr3)Ru, Cp*Rh, Cp*Ir] were prepared by reaction of [Cp*Ru(,-OMe)]2 with Me3SiCl and subsequent addition of [LMCl2]2. The complexes [Cp*Ru(,-Cl)3Ru(cymene)] and [Cp*Ru(,-Cl)3IrCp*] were characterized by single-crystal X-ray analyses. In crossover experiments with [Cp*Rh(,-Cl)3RuCl(PPh3)2] and [Cp*Ru(,-Cl)3Ru(1,3,5-C6H3iPr3)] in CD2Cl2, a dynamic equilibrium with the complexes [Cp*Rh(,-Cl)3RuCp*] and [(1,3,5-C6H3iPr3)Ru(,-Cl)3RuCl(PPh3)2] was rapidly established, demonstrating the kinetic lability of the triple chloro bridge. Upon reaction of [Cp*Rh(,-Cl)3RuCp*] with benzene, the ionic complex [Cp*Ru(C6H6)][Cp*RhCl3] was formed, which was characterized by X-ray crystallography. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006) [source] The Synthesis and Characterisation of Bis(phosphane)-Linked (6 - p -Cymene)ruthenium(II),Borane CompoundsEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 23 2005Adrian B. Chaplin Abstract The reaction of [(,6 - p -cymene)RuCl2]2 with some bis(phosphane) ligands (dppm, dppe, dppv, dppa, dpp14b, dppf) has been investigated. In general mixtures of products were obtained, although the pendant phosphane complexes [(,6 - p -cymene)RuCl2(,1 -dppv)] and [(,6 - p -cymene)RuCl2(,1 -dppa)] were isolated and characterized in the solid state by X-ray diffraction. The later complex was obtained in lower yield and undergoes an equilibration reaction resulting in the formation of a dimeric species, where the dppa bridges two ruthenium centres, and uncoordinated phosphane; the bridging species was also structurally characterised in the solid state. In contrast, the reaction of [(,6 - p -cymene)RuCl2(PPh3)] with dppa in the presence of [NH4]PF6 results in the formation of [(,6 - p -cymene)RuCl(PPh3)(,1 -dppa)]PF6, which is stable in solution. A series of linked ruthenium,borane complexes, viz. [(,6 - p -cymene)RuCl2(,1 -phosphane-BH3)] (phosphane = dppm, dppe, dppv, dppa, dpp14b, dppf) and [(,6 - p -cymene)RuCl(PPh3)(,1 -dppa-BH3)]PF6 have been prepared from isolated pendant phosphane complexes, those generated in situ, or from a preformed phosphane,borane adduct. The solid-state structures of [(,6 - p -cymene)RuCl2(,1 -dppm-BH3)], [(,6 - p -cymene)RuCl2(,1 -dppe-BH3)] and [(,6 - p -cymene)RuCl2(,1 -dppv-BH3)] have been determined by X-ray diffraction analysis. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005) [source] Stable Nickel Catalysts for Fast Norbornene Polymerization: Tuning ReactivityEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 19 2005Juan A. Casares Abstract The air-stable complexes trans -[Ni(C6Cl2F3)2L2] (L = SbPh3, 1; AsPh3, 2; AsCyPh2, 3; AsMePh2, 4; PPh3, 5) have been synthesized by arylation of [NiBr2(dme)] (dme = 1,2-dimethoxyethane) in the presence of the corresponding ligand L (for compounds 1,4) or by ligand substitution starting from 1 (for compound 5). The structures of 1, 2, and 5 have been determined by X-ray diffraction and show an almost perfect square-planar geometry in all cases. Their catalytic activity in insertion polymerization of norbornene have been tested showing a strong dependence of the yield and molecular mass of the polymer on the ligand used and the solvent. High yield and high molecular mass values are obtained using complexes with ligands easy to displace from NiII (SbPh3 is the best) and noncoordinating solvents. Complexes 1,3 are suggested as convenient bench-catalysts to have available in the lab. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005) [source] Reactions of K2[Fe(CO)3(PPh3)]: Reductive Sb,Sb Coupling with Ph2SbCl To Form trans -[Fe(CO)3(PPh3)(Sb2Ph4)] and Salt Metathesis with Me3SbCl2 To Yield trans -[Fe(CO)3(PPh3)(SbMe3)]EUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 1 2005Ingo-Peter Lorenz Abstract In contrast to the ferrate K2[Fe(CO)4], the phosphane-substituted ferrate K2[Fe(CO)3(PPh3)] (1) reacts with the stibane derivative Ph2SbCl by metal-assisted reductive Sb,Sb coupling to give the distibane complex trans -[Fe(CO)3(PPh3)(Sb2Ph4)] (3). The distibane ligand in 3 is terminally ,1 -coordinated trans to the phosphane ligand. However, the stiborane derivative Me3SbCl2 reacts with 1 in a metathetical substitution reaction to form the monostibane complex trans -[Fe(CO)3(PPh3)(SbMe3)] (5). Both compounds have been characterized by spectroscopic (IR, NMR, MS), analytical (C, H) and X-ray diffraction analyses. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005) [source] Synthesis of (Vinylidene)- and (Cyclopropenyl)ruthenium Complexes Containing a Tris(pyrazolyl)borato (Tp) LigandEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 23 2004Yih-Hsing Lo Abstract A convenient high-yield route to [Ru(C,C,Ph)(Tp)(PPh3)2] [2; Tp = HB(pz)3, pz = pyrazolyl] has been found through the intermediacy of [RuCl2(Hpz)2(PPh3)2] (1). This complex is readily obtained on treatment of [RuCl2(PPh3)3] with 2 equiv. of pyrazole in boiling THF. The molecular structures of complexes 1 and 2 have been confirmed by single-crystal X-ray diffraction analysis. A number of new cationic vinylidene complexes [Ru{=C=C(Ph)CH2R}(Tp)(PPh3)2]+ [3a, R = CN; 3b, R = HC=CH2; 3c, R = CH=C(CH3)2; 3d, R = Ph; 3e, R = C(O)OMe] have been prepared by electrophilic addition of organic halides to complex 2. The deprotonation reaction of 3a yields the cyclopropenyl complex 4a. One phosphane ligand of 4a is remarkably labile, being replaced by donor ligands L to yield diastereomeric mixtures of the cyclopropenyl complexes 5a,5d mostly in an approximate 4:1 ratio. The cyclopropenyl rings in 4a and 5a are susceptible to ring opening by I2. In addition, treatment of 4a with nBuNC in the presence of MeOH results in substitution of a phosphane ligand by nBuNC followed by protonation of the three-membered ring by MeOH. This is then followed by addition of methoxide to give the vinyl ether complex [Ru{C(OMe)=C(Ph)CH2CN}(Tp)(PPh3)(nBuNC)] (8a). (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004) [source] | |||||||||||||||||||||||||