Reaction between Os(SnClMe2)(κ2-S2CNMe2)(CO)(PPh3)2 and either LiSnMe3 or KSnPh3 produces the distannyl complexes, Os(SnMe2SnMe3)(κ2-S2CNMe2)(CO)(PPh3)2 (1) or Os(SnMe2SnPh3)(κ2-S2CNMe2)(CO)(PPh3)2 (3), respectively. Similarly, reaction between Os(SnClMe2)Cl(CO)2(PPh3)2 (6) and KSnPh3 produces the distannyl complex, Os(SnMe2SnPh3)Cl(CO)2(PPh3)2 (7). In the 119Sn NMR spectra of these stable osmium(II) distannyl complexes both the α-Sn and β-Sn atoms show well-resolved 119Sn-119Sn and 119Sn-117Sn coupling. Each of these three distannyl complexes can be selectively functionalised at the α-Sn atom by reaction with SnCl2Me2 giving Os(SnClMeSnMe3)(κ2-S2CNMe2)(CO)(PPh3)2 (2), Os(SnClMeSnPh3)(κ2-S2CNMe2)(CO)(PPh3)2 (4), and Os(SnClMeSnPh3)Cl(CO)2(PPh3)2 (8), respectively. Treatment of compounds 3 or 7 with iodine also cleaves one α-methyl group, selectively, to give Os(SnIMeSnPh3)(κ2-S2CNMe2)(CO)(PPh3)2 (5), or Os(SnIMeSnPh3)Cl(CO)2(PPh3)2 (9). Crystal structures for complexes 3 and 7 have been determined. 相似文献
RuHCl(CO)2(PPh3)2 reacts with ethylene under mild conditions (25 psi, 80°C) to yield a propionyl derivative RuCl(C[O]C2H5)(CO)(PPh3)2 which is believed to be coordinatively unsaturated. Unlike the acetyl analogue, RuCl[C[O]C2H5(CO)-(PPh3)2 does not isomerize to RuCl(C2H5)(CO)2(PPh3)2 in solution. Under one atmosphere of carbon monoxide, RuCl(C[O]C2H5(CO)(PPh3)2 exists in equilibrium with two species believed to be RuCl(C[O]C2H5)(CO)2(PPh3)2 and [Ru(C[O]C2H5)(CO)3(PPh3)2]Cl. RuCl(C[O]C2H5)(CO)(PPh3)2 reacts with CO/ AgClO4 to give mer-[Ru(C[O]C2H5)(CO)3(PPh3)2]ClO4, p-tolylisocyanide (RNC) and NaClO4 to give cis-[Ru(C[O]C2H5)(CO)(CNR)2(PPh3)2ClO4, and hydrochloric acid to yield the hydroxycarbene complex, RuCl2(CO)(C[OH]C2H5)(PPh3)2. 相似文献
The compounds Ru3(CO)9(SnPh3)2(NCMe)(μ-H)2 (1), Ru3(CO)10(SnPh3)2(μ-H)2 (2), Ru(CO)4(SnPh3)2 (3) and Ru(CO)4(SnPh3)(H) (4) were obtained from the reaction of Ru3(CO)10(NCMe)2 with HSnPh3 in hexane solvent. Compounds 1, 3 and the new compound Ru3(CO)7(SnPh3)3(NCMe)2(μ-H)3 (5) were obtained from reaction of Ru3(CO)10(NCMe)2 with HSnPh3 in a CH2Cl2 and MeCN solvent mixture. Compound 2 and the new compound Ru3(CO)9(SnPh3)3(μ-H)3 (6) were obtained from reactions of 1 and 5 with CO, respectively. Compounds 2 and 6 eliminated benzene when heated to yield Ru3(CO)10(μ-SnPh2)2 (7) and Ru3(CO)9(μ-SnPh2)3 (8) which contain bridging SnPh2 ligands. Compound 7 was found to react with to yield the adduct, (9) in 59% yield by the addition of groups to two of the Ru-Sn bonds to the bridging SnPh2 ligands. Fenske-Hall molecular orbital calculations were performed to provide an understanding of the metal-metal bonding in the clusters of 7 and 9. Compounds 1, 2, 5, 6, 7 and 9 were characterized structurally by single crystal X-ray diffraction analysis. 相似文献
Ph2P(O)C(S)N(H)R (R Me, Ph) reacts with M(CO)3(η5-C5H5)Cl (M Mo, W) in the presence of Et3N to give M(CO)2(η5-C5H5)(Ph2P(O)C(S)NR). The deprotonated ligand coordinates in a bidentate manner through N and S to give a four-membered ring system. M(CO)3(PPh3)2Cl2 (M Mo, W) reacts with Ph2P(O)C(S)N(H)R (R Me, Ph) in the presence of Et3N to give complexes in which the central metal atoms are seven coordinate through two ligands bonded via O and S to form five-membered ring systems, one PPh3, and two CO groups. The complexes were characterised by elemental analyses, IR, 1H NMR, and 31P NMR spectroscopy, and an X-ray structural analysis of Mo(CO)2(PPh3)(Ph2P(O)C(S)NPh)2 · CH2Cl2. 相似文献
Reaction between Os(CO)2(PPh3)3 and Me3SnH produces Os(SnMe3)H(CO)2(PPh3)2 (1). Multinuclear NMR studies of solutions of 1 reveal the presence of four geometrical isomers, the major one being that with mutually cis triphenylphosphine ligands and mutually trans CO ligands. Os(SnMe3)H(CO)2(PPh3)2 undergoes a redistribution reaction, at the trimethylstannyl ligand, when treated with Me2SnCl2 giving Os(SnMe2Cl)H(CO)2(PPh3)2 (2). Solutions of 2 again show the presence of four isomers but now the major isomer is that with mutually trans triphenylphosphine ligands and mutually cis CO ligands. The redistribution reaction of 1 with SnI4 produces Os(SnMeI2)H(CO)2(PPh3)2 (3) which exists in solution as only one isomer, that with mutually trans triphenylphosphine ligands and mutually trans CO ligands. Treatment of 3 with I2 cleaves the Os-H bond with retention of geometry giving Os(SnMeI2)I(CO)2(PPh3)2 (4). The crystal structure of 4 has been determined. No isomerization of the trans dicarbonyl complex 4 occurs when 4 is heated, instead there is a formal loss of “MeSnI” and formation of OsI2(CO)2(PPh3)2 (5). 相似文献
The thiocarbonyl analogue of Vaska’s compound is produced in high yield by first treating IrCl(CO)(PPh3)2 with CS2 and methyl triflate to give [Ir(κ2-C[S]SMe)Cl(CO)(PPh3)2]CF3SO3 (1), secondly, reacting 1 with NaBH4 to give IrHCl(C[S]SMe)(CO)(PPh3)2 (2), and finally heating 2 to induce elimination of both MeSH and CO to produce IrCl(CS)(PPh3)2 (3). When IrCl(CS)(PPh3)2 is treated with Hg(CHCHPh)2 the novel 2-iridathiophene, Ir[SC3H(Ph-3)(CHCHPh-5)]HCl(PPh3)2 (4) is produced. The X-ray crystal structure of the iodo-derivative of 4, Ir[SC3H(Ph-3)(CHCHPh-5)]HI(PPh3)2 (5) confirms the unusual 2-metallathiophene structure. Treatment of IrCl(CS)(PPh3)2 with Hg(CHCPh2)2 produces both a coordinatively unsaturated 1-iridaindene, Ir[C8H5(Ph-3)]Cl(PPh3)2 (6) and a chelated dithiocarboxylate complex, Ir(κ2-S2CCHCPh2)Cl(CHCPh2)(PPh3)2 (7). X-ray crystal structure determinations for 6 and 7 are reported. 相似文献
Detailed procedures for the syntheses of Os(CO)2(PPh3)3, Os(CO)(CNR)-(PPh3)3 (R = p-tolyl), Os(CO)(CS)(PPh3)3 and Os(CS)(CNR)(PPh3)3, together with the derived complexes Os(CO)2(CS)(PPh3)2, Os(CO)(CS)(CNR)(PPh3)2, Os(η2-C2H4)(CO)(CNR)(PPh3)2, Os(η2-C2H4)(CO)(CS)(PPh3)2, Os(η2CS2)(CO)2-(PPh3)2, Os(η2CS2)(CO)(CS)(PPh3)2, Os(η2-CS2)(CO)(CNR)(PPh3)2, Os(η2PhC2Ph)(CO)2(PPh3)2 and OsH(C2Ph)(CO)2(PPh3)2 are described. 相似文献
Reaction between the dichloroboryl complex, Os(BCl2)Cl(CO)(PPh3)2, and water replaces both chloride substituents on the boryl ligand, without cleavage of the Os---B bond, giving yellow Os[B(OH)2]Cl(CO)(PPh3)2 (1). Compound 1 can be regarded as an example of a ‘metalla–boronic acid’ (LnM---B(OH)2) and in the solid state, X-ray crystal structure determination reveals that molecules of 1 are tetragonal pyramidal in geometry (Os---B, 2.056(3) Å) and are arranged in pairs, as hydrogen-bonded dimers. This same arrangement is found in the crystalline state for simple boronic acids. Reaction between the dichloroboryl complex, Os(BCl2)Cl(CO)(PPh3)2, and methanol and ethanol produces yellow Os[B(OMe)2]Cl(CO)(PPh3)2 (2a) and yellow Os[B(OEt)2]Cl(CO)(PPh3)2 (2b), respectively. The crystal structure of 2b reveals a tetragonal pyramidal geometry with the diethoxyboryl ligand in the apical site and with an Os---B bond distance of 2.081(5) Å. Reaction between Os(BCl2)Cl(CO)(PPh3)2, and N,N′-dimethyl-o-phenylenediamine and N,N′-dimethyl-ethylenediamine produces yellow
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(5) and yellow
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(6), respectively. Compounds 1, 2a, 2b, 5, and 6 all react with carbon monoxide to give the colourless, six-coordinate complexes Os[B(OH)2]Cl(CO)2(PPh3)2 (3), Os[B(OMe)2]Cl(CO)2(PPh3)2 (4a), Os[B(OEt)2]Cl(CO)2(PPh3)2 (4b),
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(7), and
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(8), respectively, but in the case of 6 only, this CO uptake is easily reversible. The crystal structure of 5 is also reported. 相似文献
The ruthenium-tin complex, [Ru2(CO)4(SnPh3)2(μ-pyS)2] (1), the main product of the oxidative-addition of pySSnPh3 to Ru3(CO)12 in refluxing benzene, is [Ru(CO)2(pyS)(SnPh3)] synthon. It reacts with PPh3 to give [Ru(CO)2(SnPh3)(PPh3)(κ2-pyS)] (2) and further with Ru3(CO)12 or [Os3(CO)10(NCMe)2] to afford the butterfly clusters [MRu3(CO)12(SnPh3)(μ3-pyS)] (3, M=Ru; 4, M=Os). Direct addition of pySSnPh3 to [Os3(CO)10(NCMe)2] at 70 °C gives [Os3(CO)9(SnPh3)(μ3-pyS)] (5) as the only bimetallic compound, while with unsaturated [Os3(CO)8{μ3-PPh2CH2P(Ph)C6H4}(μ-H)] the previously reported [Os3(CO)8(μ-pyS)(μ-H)(μ-dppm)] (6) and the new bimetallic cluster [Os3(CO)7(SnPh3){μ-Ph2PCH2P(Ph)C6H4}(μ-pyS)[(μ-H)] (7) are formed at 110 °C. Compounds 1, 2, 4, 5 and 7 have been characterized by X-ray diffraction studies. 相似文献
Abstraction of iodide from Ir(CF3)ClI(CO)(PPh3)2 (1) by AgSbF6 in the presence of acetonitrile yields the cationic complex [Ir(CF3)Cl(MeCN)(CO)(PPh3)2]+ [SbF6]− (2). The acetonitrile group of 2 is readily displaced, and 2 reacts with para-tolyl isocyanide to yield [Ir(CF3)Cl(CN-p-tolyl)(CO)(PPh3)2]+ [SbF6]− (3). The addition of NaOMe to 3 results in the methoxyester complex Ir(CF3)(COOMe)Cl(CN-p-tolyl) (PPh3)2 (4). The acetonitrile ligand of 2 is also displaced by anions, including H−. Thus, 2 reacts with LiEt3BH to give Ir(CF3)HCl(CO)(PPh3)2 (5), in which the hydrido and trifluoromethyl ligands are mutually trans. In contrast, the addition of excess NaBH4 to 2 affords the novel dihydrido complex trans-Ir(CF3)H2(CO)(PPh3)2 (6). Investigations into the potential use of 5 and 6 as precursors of an iridium(I) complex such as Ir(CF3)(CO)(PPh3)2 are also described. 相似文献
Reaction between Os(CO)2(PPh3)3 and 3,3-diphenylcyclopropene under quartz-halogen irradiation leads to C(sp2)-H bond activation and the formation of the 3,3-diphenylcyclopropenyl complex, OsH[C3H(Ph-2)2](CO)2(PPh3)2 (1). When complex 1 is heated there is ring-opening of the cyclopropene ring and rearrangement to the 3-phenylindenyl complex, OsH[C9H6(Ph-3)](CO)2(PPh3)2 (2). Compound 1 reacts with HCl forming the 2,2-diphenylcyclopropyl complex, OsCl[C3H3(Ph-2)2](CO)2(PPh3)2 (3). Reaction of either 1 or 3 with excess HCl leads to reversible formation of the hydroxycarbene complex, OsCl2[C(OH)C3H3(Ph-2)2](CO)(PPh3)2 (4), through protonation of the acyl group formed by a migratory insertion reaction involving a carbonyl ligand and the σ-bound 2,2-diphenylcyclopropanyl ligand. An X-ray crystal structure determination of 2 is reported. 相似文献
The oxidative addition of CH3I to planar rhodium(I) complex [Rh(TFA)(PPh3)2] in acetonitrile (TFA is trifluoroacetylacetonate) leads to the formation of cationic, cis-[Rh(TFA)(PPh3)2(CH3)(CH3CN)][BPh4] (1), or neutral, cis-[Rh(TFA)(PPh3)2(CH3)(I)] (4), rhodium(III) methyl complexes depending on the reaction conditions. 1 reacts readily with NH3 and pyridine to form cationic complexes, cis-[Rh(TFA)(PPh3)2(CH3)(NH3)][BPh4] (2) and cis-[Rh(TFA)(PPh3)2(CH3)(Py)][BPh4] (3), respectively. Acetylacetonate methyl complex of rhodium(III), cis-[Rh(Acac)(PPh3)2(CH3)(I)] (5), was obtained by the action of NaI on cis-[Rh(Acac)(PPh3)2(CH3)(CH3CN)][BPh4] in acetone at −15 °C. Complexes 1-5 were characterized by elemental analysis, 31P{1H}, 1H and 19F NMR. For complexes 2, 3, 4 conductivity data in acetone solutions are reported. The crystal structures of 2 and 3 were determined. NMR parameters of 1-5 and related complexes are discussed from the viewpoint of their isomerism. 相似文献
The reaction of IrRu3(CO)13(μ-H), 1 with HSnPh3 in hexane solvent at reflux has provided the new mixed metal cluster compounds Ir2Ru2(CO)11(SnPh3)(μ-H)3, 2 and IrRu3(CO)11(SnPh3)3(μ-H)4, 3 containing SnPh3 ligands. Compound 2 which was obtained in low yield (3%) contains one SnPh3, two iridium atoms and two ruthenium atoms. The increase in the number of iridium atoms must have resulted from a metal–metal
exchange process. The major product 3 (19% yield) contains an open cluster of one iridium and three ruthenium atoms with three SnPh3 ligands and four hydride ligands. Both compounds were characterized structurally by single crystal X-ray diffraction analysis. 相似文献
The iridium(I) complex [Ir(CO2Me)(CO)2(PPh3)2] undergoes a transesterification reaction with the alcohols CH2C(R)CH2OH (R = H, Me), MeCCCH2CH2OH, and HOCH2CH2OH to afford the complexes [Ir(CO2CH2CH2CMe)(CO)2(PPh3)2] and [Ir(CO2CH2CH2OH)(CO)2(PPh3)2], respectively. In contrast the acetylenic alcohol HCCCH2CH2OH gives [Ir(CCCH2CH2OH)(CO)PPh3)2]. Some reactions of the new complexes are described. 相似文献
Treatment of [Ru(CHCHCH2PPh3)X(CO)(PPh3)2]+ (X=Cl, Br) with KTp (Tp=hydridotris(pyrazolyl)borate) and NaBPh4 produced [TpRu(CHCHCH2PPh3)(CO)(PPh3)]BPh4. Reaction of RuHCl(CO)(PPh3)3 with HCCCH(OEt)2 produced Ru(CHCHCH(OEt)2)Cl(CO)(PPh3)2, which reacted with KTp to give TpRu(CHCHCHO)(CO)(PPh3). Treatment of [TpRu(CHCHCH2PPh3)(CO)(PPh3)]BPh4 with NaN(SiMe3)2 and benzaldehyde produced TpRu(CHCHCHCHPh)(CO)(PPh3). The later complex was also produced when TpRu(CHCHCHO)(CO)(PPh3) was treated with PhCH2PPh3Cl/NaN(SiMe3)2. The bimetallic complex [TpRu(CO)(PPh3)]2(μ-CHCHCHCHC6H4CHCHCHCH) was obtained from the reaction of [TpRu(CHCHCH2PPh3)(CO)(PPh3)]BPh4 with NaN(SiMe3)2 and terephthaldicarboxaldehyde. 相似文献
The chemical or electrochemical reduction of the trifluoroacetyl complex Co(CO)3(PPh3)(COCF3) involves a single electron transfer yielding trifluoromethyl radical and an anionic cobalt carbonyl complex. The mechanism is proposed to involve electron transfer followed by initial dissociation of either a carbonyl or phosphine ligand from the 19-electron [Co(CO)3(PPh3)(COCF3)]− anion. The resulting 17-electron intermediate undergoes subsequent one-electron reductive elimination of trifluoromethyl radical by homolytic cleavage of the carbon-carbon bond of the trifluoroacetyl group. The radical can be trapped by either benzophenone anion, forming the anion of α-(trifluoromethyl)benzhydrol, or Bu3SnH, yielding CF3H. The ultimate organometallic product is an 18-electron anion, either [Co(CO)4]− or [Co(CO)3(PPh3)]−, depending upon which ligand is initially lost. Fluorine-containing products were identified and quantitated by 19F NMR while cobalt-containing products were determined by IR. 相似文献
The new complex Ru3(CO)9(PPh2H)3 (I) was prepared by the direct thermal reaction of Ru3(CO)12 with PPh2 H and was spectroscopically characterized. Irradiation of I with λ ≥ 300 nm leads to the formation of Ru2(μ-PPh2)2(CO)6 (II) and three new phosphido-bridged complexes, Ru3(μ-H)2(μ-PPh2)2(CO)8 (III), Ru3(μ-H)2(μ-PPh2)2(CO)7(PPh2H) (IV) and Ru3(μ-H)(μ-PPh2)3(CO)7 (V). These complexes have been characterized spectroscopically and Ru3 (μ-H)(μ-PPh2)3(CO)7 by a complete single crystal X-ray structure determination. It crystallizes in the space group P21/n with a 20.256(3), b 22.418(6), c 20.433(5) Å, β 112.64(2)°, V 8564(4) Å3, and Z = 8. Diffraction data were collected on a Syntex P21 automated diffractometer using graphite-monochromatized Mo-Kα radiation, and the structure was refined to RF 4.76% and RwF 5.25% for the 8,847 independent reflections with F0 > 6σ(F0). The structure consists of a triangular array of Ru atoms with seven terminal carbonyl ligands, three bridging diphenylphosphido ligands which bridge each of the RuRu bonds, and the hydride ligand which bridges one RuRu bond. Complex IV was also shown to give V upon photolysis and is thus an intermediate in the photoinduced formation of V from I. 相似文献
The complexes [Ru3(CO)7(PPh2)2(C6H4)] and [Ru2(CO)5(PPh3)(μ-PPh2)(μ-OCPh)] were obtained by pyrolysis of [Ru3(CO)9(PPh3)3] and tested as catalysts for the hydrogenation of cyclohexene and 2-cyclohexen-1-one. The structure of [Ru2(CO)5(PPh3)(μ-PPh2)(μ-OCPh)] was established by a single crystal X-ray diffraction study. 相似文献
Syntheses and Structure of Chiral Metallatetrahedron Complexes of the Type [Re2(M1PPh3)(M2PPh3)(μ‐PCy2)(CO)7C≡CPh] (M1 = Ag, Au; M2 = Cu, Ag, Au) From the reaction of Li[Re2(μ‐H)(μ‐PCy2)(CO)7(C(Ph)O)] ( 1 ) with Ph3AuC≡CPh both benzaldehyde and the trinuclear complex Li[Re2(AuPPh3)(μ‐PCy2)(CO)7C≡CPh] ( 2a ) were obtained in high yield. The complex anion was isolated as its PPh4‐salt 2b . The latter reacts with coinage metal complexes PPh3M2Cl [M2 = Cu, Ag, Au] to give chiral heterometallatetrahedranes of the general formula [Re2(AuPPh3)(M2PPh3)(μ‐PCy2)(CO)7C≡CPh] (M2 = Cu 3a , Ag 3b , Au 3c ). The corresponding complex [Re2(AgPPh3)2(μ‐PCy2)(CO)7C≡CPh] ( 3d ) is obtained from the reaction of [Re2(AgPPh3)2(μ‐PCy2)(CO)7Cl] ( 4 ) with LiC≡CPh. 3d undergoes a metathesis reaction in the presence of PPh3CuCl giving [Re2(AgPPh3)(CuPPh3)(μ‐PCy2)(CO)7C≡CPh] ( 3e ) and PPh3AgCl. Analogous metathesis reactions are observed when 3c is reacted with PPh3AgCl or PPh3CuCl giving 3a or 3b , respectively. The reaction of 1 with PPh3AuCl gives benzaldehyde and Li[Re2(AuPPh3)(μ‐PCy2)(CO)7Cl] ( 5a ) which upon reaction with PhLi forms the trinuclear complex Li[Re2(AuPPh3)(μ‐PCy2)(CO)7Ph] ( 6a ). Again this complex was isolated as its PPh4‐salt 6b . In contrast to 2b , 6b reacts with one equivalent of Ph3PAuCl by transmetalation to give Ph3PAuPh and PPh4[Re2(AuPPh3)(μ‐PCy2)(CO)7Cl] ( 5b ). The X‐ray structures of the compounds 3a , 3b , 3e and 4 are reported. 相似文献
Summary The reaction of previously reported RhI and IrI cationic complexes towards carbon monoxide and triphenylphosphine has been studied. Carbonyl rhodium(I) mixed complexes of the formulae [Rh(CO)L2(PPh3)]ClO4, (L=tetrahydrothiophene(tht), trimethylene sulfide(tms), SMe2, or SEt2), [(CO)(PPh3)Rh{-(L-L)}2Rh(PPh3)(CO)](ClO4)2 (L-L= 2,2,7,7-tetramethyl-3,6-dithiaoctane (tmdto), (MeS)2(CH2)3 (dth), or 1,4-dithiacyclohexane (dt), [Rh(CO)L(PPh3)2]ClO4 (L= tht, tms, SMe2, or SEt2), and carbonyl iridium(I) complexes of the formulae [Ir(CO)2(COD)(PPh3)]ClO4, [Ir(CO)(COD)(PPh3)2]ClO4, [(CO)(COD)(PPh3) Ir{-(L-L)} Ir(PPh3)(COD)(CO)](ClO4)2 (L-L = tmdto or dt), [(CO)2 (PPh3)Ir(-tmdto)Ir(PPh3)(CO)2](ClO4)2, [(CO)2(PPh3) Ir(-dt)2Ir(PPh3)(CO)2](ClO4)2, were prepared by different synthetic methods. 相似文献
