The reactions of [RuHCl(CO)(PPh3)3] and [(C6H6)RuCl2]2 with 2-benzoylpyridine have been examined, and two novel ruthenium(II) complexes – [RuCl(CO)(PPh3)2(C5H4NCOO)] and [RuCl2(C12H9NO)2] – have been obtained. The compounds have been studied by IR and UV–Vis spectroscopy, and X-ray crystallography. The molecular orbital diagrams of the complexes have been calculated with the density functional theory (DFT) method. The spin-allowed singlet–singlet electronic transitions of the compounds have been calculated with the time-dependent DFT method, and the UV–Vis spectra of the compounds have been discussed on this basis. 相似文献
A new ruthenium-rhodium mixed-metal cluster HRuRh3(CO)12 and its derivatives HRuRh3(CO)10(PPh3)2 and HRuCo3(CO)10(PPh3)2 have been synthesized and characterized. The following crystal and molecular structures are reported: HRuRh3(CO)12: monoclinic, space group P21/c, a 9.230(4), b 11.790(5), c 17.124(9) Å, β 91.29(4)°, Z = 4; HRuRh3(CO)10(PPh3)2·C6H14: triclinic, space group P, a 11.777(2), b 14.079(2), c 17.010(2) Å, α 86.99(1), β 76.91(1), γ 72.49(1)°, Z = 2; HRuCo3(CO)10(PPh3)2·CH2Cl2: triclinic, space group P, a 11.577(7), b 13.729(7), c 16.777(10) Å, α 81.39(4), β 77.84(5), γ 65.56°, Z = 2. The reaction between Rh(CO)4? and (Ru(CO)3Cl2)2 tetrahydrofuran followed by acid treatment yields HRuRh3(CO)12 in high yield. Its structural analysis was complicated by a 80–20% packing disorder. More detailed structural data were obtained from the fully ordered structure of HRuRh3(CO)10(PPh3)2, which is closely related to HRuCo3(CO)10(PPh3)2 and HFeCo3(CO)10(PPh3)2. The phosphines are axially coordinated. 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
A high-yield synthesis of trans-RuCl2(CS)(H2O)(PPh3)2 from RuCl2(PPh3)3 and CS2 is described. The coordinated water molecule is labile, and introduction of CNR (R p-toyl or p-chlorophenyl) leads to yellow trans-RuCl2(CS)(CNR)(PPh3)2, which isomerises thermally to colourless cis-RuCl2(CS)(CNR)(PPh3)2. Reaction of AgClO4 with cis-RuCl2(CS)(CNR)(PPh3)2 gives [RuCl(CS)(CNR)(H2O)(PPh3)2]+, from which [RuCl(CS)(CO)(CNR)(PPh3)2]+ and [RuCl(CS)(CNR)2(PPh3)2]+ are derived. Reaction of trans-RuCl2(CS)(H2O)(PPh3)2 with sodium formate gives Ru(η2-O2CH)Cl(CS)(PPh3)2, which undergoes decarboxylation in the presence of (PPh3) to give RuHCl(CS)(PPh3)3. Ru(η2-O2CH)H(CS)(PPh3)2 and Ru(η2-O2CMe)-H(CS)(PPh3)2 are also described. 相似文献
The title compound can be prepared in good yield by heating either [Ru4(μ-H)4(CO)12] or [Au2Ru4(μ3-H)2(CO)12(PPh3)2] with [AuMe(PPh3)] in toluene. The related compound [Au3Ru4(μ3-H)(μ-dppm)(CO)12(PPh3)] has also been prepared. Both trigoldtetraruthenium clusters undergo dynamic behaviour in solution, involving intramolecular rearrangement of the metal core, as revealed by variable temperature NMR studies. The crystal structure of [Au3Ru4(μ3-H)(CO)12(PPh3)3] has been established by an X-ray diffraction study. The metal atom core comprises a trigonal bipyramidal AuRu4 unit with two AuRu2 faces capped by gold atoms. 相似文献
The objective of the present work was to synthesize mononuclear ruthenium complex [RuCl2(CO)2{Te(CH2SiMe3)2}2] (1) by the reaction of Te(CH2SiMe3)2 and [RuCl2(CO)3]2. However, the stoichiometric reaction affords a mixture of 1 and [RuCl2(CO){Te(CH2SiMe3)2}3] (2). The X-ray structures show the formation of the cis(Cl), cis(C), trans(Te) isomer of 1 and the cis(Cl), mer(Te) isomer of 2. The 125Te NMR spectra of the complexes are reported. The complex distribution depends on the initial molar ratio of the reactants. With an excess of [RuCl2(CO)3]2 only 1 is formed. In addition to the stoichiometric reaction, a mixture of 1 and 2 is observed even when using an excess of Te(CH2SiMe3)2. Complex 1 is, however, always the main product. In these cases the 125Te NMR spectra of the reaction solution also indicates the presence of unreacted ligand. 相似文献
A reinvestigation of the reaction of Ir(CO)Cl(PPh3)2, 1 with HSnPh3 has revealed that the oxidative-addition product Ir(CO)Cl(PPh3)2(H)(SnPh3), 2 has the H and SnPh3 ligands in cis-related coordination sites. Compound 2 reacts with a second equivalent of HSnPh3 by a Cl for H ligand exchange to yield the new compound H2Ir(CO)(SnPh3)(PPh3)2, 3. Compound 3 contains two cis- related hydride ligands. Under an atmosphere of CO, 1 reacts with HSnPh3 to replace the Cl ligand with SnPh3 and one of the PPh3 ligands with a CO ligand and also adds a second equivalent of CO to yield the 5-coordinate complex Ir(CO)3(SnPh3)(PPh3), 4. Compound 4 reacts with HSnPh3 by loss of CO and oxidative addition of the Sn-H bond to yield the 6-coordinate complex HIr(CO)2(SnPh3)2(PPh3), 5 that contains two trans-positioned SnPh3 ligands. 相似文献
The reactivity of [Pt2(μ-S)2(PPh3)4] towards [RuCl2(η6-arene)]2 (arene=C6H6, C6Me6, p-MeC6H4Pri=p-cymene), [OsCl2(η6-p-cymene)]2 and [MCl2(η5-C5Me5)]2 (M=Rh, Ir) have been probed using electrospray ionisation mass spectrometry. In all cases, dicationic products of the type [Pt2(μ-S)2(PPh3)4ML]2+ (L=π-hydrocarbon ligand) are observed, and a number of complexes have been prepared on the synthetic scale, isolated as their BPh4− or PF6− salts, and fully characterised. A single-crystal X-ray structure determination on the Ru p-cymene derivative confirms the presence of a pseudo-five-coordinate Ru centre. This resists addition of small donor ligands such as CO and pyridine. The reaction of [Pt2(μ-S)2(PPh3)4] with RuClCp(PPh3)2 (Cp=η5-C5H5) gives [Pt2(μ-S)2(PPh3)4RuCp]+. In addition, the reaction of [Pt2(μ-S)2(PPh3)4] with the related carbonyl complex [RuCl2(CO)3]2, monitored by electrospray mass spectrometry, gives [Pt2(μ-S)2(PPh3)4Ru(CO)3Cl]+. 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
Treatment of [RuCl2(PPh3)3] with 2 equiv. HimtMPh (HimtMPh?=?1-(4-methyl-phenyl)-imidazole-2-thione) in the presence of MeONa afforded cis-[Ru(κ2-S,N-imtMPh)2(PPh3)2] (1), while interaction of [RuCl2(PPh3)3] and 2 equiv. HimtMPh in tetrahydrofuran (THF) without base gave [RuCl2(κ1-S-HimtMPh)2(PPh3)2] (2). Treatment of [RuHCl(CO)(PPh3)3] with 1 equiv. HimtMPh in THF gave [RuHCl(κ1-S-HimtMPh)(CO)(PPh3)2] (3), whereas reaction of [RuHCl(CO)(PPh3)3] with 1 equiv. of the deprotonated [imtMPh]? or [imtNPh]? (imtNPh?=?1-(4-nitro-phenyl)-2-mercaptoimidazolyl) gave [RuH(κ2-S,N-imtRPh)(CO)(PPh3)2] (R?=?M 4a, R?=?N 4b). The ruthenium hydride complexes 4a and 4b easily convert to their corresponding ruthenium chloride complexes [RuCl(κ2-S,N-imtMPh)(CO)(PPh3)2] (5a) and [RuCl(κ2-S,N-imtNPh)(CO)(PPh3)2] (5b), respectively, in refluxing CHCl3 by chloride substitution of the RuH. Photolysis of 5a in CHCl3 at room temperature afforded an oxidized product [RuCl2(κ2-S,N-imtMPh)(PPh3)2] (6). Reaction of 6 with excess [imtMPh]? afforded 1. The molecular structures of 1·EtOH, 3·C6H14, 4b·0.25CH3COCH3, and 6·2CH2Cl2 have been determined by single-crystal X-ray crystallography. 相似文献
In addition to well-known dinuclear phenylselenolato palladium complexes, the reaction of [PdCl2(PPh3)2] and NaSePh affords small amounts of novel trinuclear and hexanuclear complexes [Pd3Se(SePh)3(PPh3)3]Cl (1) and [Pd6Cl2Se4(SePh)2(PPh3)6] (2). Complex 1 is triclinic, P1?, a=13.6310(2), b=16.2596(2), c=16.9899(3) Å, α=83.1738(5), β=78.9882(5), γ=78.7635(5)°. Complex 2 is monoclinic, C2/c, a=25.7165(9), b=17.6426(8), c=27.9151(14) Å, β=110.513(2)°. There are no structural forerunners for 1, but the hexanuclear complex 2 is isostructural with [Pd6Cl2Te4(TeR)2(PPh3)6] (R=Ph, C4H3S) that have been observed as one of the products in the oxidative addition of R2Te2 to [Pd(PPh3)4]. Mononuclear palladium complexes may play a significant role as building blocks in the formation of the polynuclear complexes. 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 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 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
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
The polymeric precursor [RuCl2(CO)2]n reacts with the ligands, P∩P (a, b) and P∩O (c, d), in 1:1 M ratio to generate six-coordinate complexes [RuCl2(CO)2(?2-P∩P)] (1a, 1b) and [RuCl2(CO)2(?2-P∩O)] (1c, 1d), where P∩P: Ph2P(CH2)nPPh2, n = 2(a), 3(b); P∩O: Ph2P(CH2)nP(O)Ph2, n = 2(c), 3(d). The complexes are characterized by elemental analyses, mass spectrometry, thermal studies, IR, and NMR spectroscopy. 1a–1d are active in catalyzed transfer hydrogenation of acetophenone and its derivatives to corresponding alcohols with turnover frequency (TOF) of 75–290 h?1. The complexes exhibit higher yield of hydrogenation products than catalyzed by RuCl3 itself. Among 1a–1d, the Ru(II) complexes of bidentate phosphine (1a, 1b) show higher efficiency than their monoxide analogs (1c, 1d). However, the recycling experiments with the catalysts for hydrogenation of 4-nitroacetophenone exhibit a different trend in which the catalytic activities of 1a, 1b, and 1d decrease considerably, while 1c shows similar activity during the second run. 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
In the presence of trialkylamine and formic acid RuCl2(PPh3)3 selectively reduces aldehydes to the corresponding alcohols at room temperature. Other reducible groups are unaffected. 相似文献
The utility of [(NHC)(PPh3)RuCl2(CHPh)] for the facile and efficient synthesis of ten complexes of the type [(NHC)(NHCewg)RuCl2(CHR)] with saturated and unsaturated NHC ligands in 85-94% isolated yield via a simple one step synthesis utilizing [AgI(NHCewg)] as NHCewg transfer reagents was demonstrated. 相似文献
