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
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
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
Reactions of [Pt2(μ-S)2(PPh3)4] with Ph3PbCl, Ph2PbI2, Ph2PbBr2 and Me3PbOAc result in the formation of bright yellow to orange solutions containing the cations [Pt2(μ-S)2(PPh3)4PbR3]+ (R3 = Ph3, Ph2I, Ph2Br, Me3) isolated as PF6− or BPh4− salts. In the case of the Me3Pb and Et3Pb systems, a prolonged reaction time results in formation of the alkylated species [Pt2(μ-S)(μ-SR)(PPh3)4]+ (R = Me, Et). X-ray structure determinations on [Pt2(μ-S)2(PPh3)4PbMe3]PF6 and [Pt2(μ-S)2(PPh3)4PbPh2I]PF6 have been carried out, revealing different coordination modes. In the Me3Pb complex, the (four-coordinate) lead atom binds to a single sulfur atom, while in the Ph2PbI adduct coordination of both sulfurs results in a five-coordinate lead centre. These differences are related to the electron density on the lead centre, and indicate that the interaction of the heterometal centre with the {Pt2S2} metalloligand core can be tuned by variation of the heteroatom substituents. The species [Pt2(μ-S)2(PPh3)4PbR3]+ display differing fragmentation pathways in their ESI mass spectra, following initial loss of PPh3 in all cases; for R = Ph, loss of PbPh2 occurs, yielding [Pt2(μ-S)2(PPh3)3Ph]+, while for R = Me, reductive elimination of ethane gives [Pt2(μ-S)2(PPh3)3PbMe]+, which is followed by loss of CH4. 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
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 reaction of Ir2(CO)6(PPh3)2 with p-substituted aryldiazoniurn salts gives the o-metalated complexes [Ir(CO)2(NHNC6H3R) (PPh3)]22+ 2BF4?. These react with KOH in ethanol to give the deprotonated derivatives, and with halogens to give halogenated derivatives by cleavage of the carbonmetal bond. 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
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
Kinetics, equilibrium and thermodynamics of interaction of CO with RuCl2(PPh3)3 (1) have been investigated in 1:1(v/v) water — 1,4-dioxan mixture in which 1 dissociates to RuCl2(PPh3)2 (1a), by losing a coordinated PPh3. The kinetics of complexation of (1a) with CO to form RuCl2(CO)(PPh3)2 (2) indicated first order dependence in [1a] and [CO]. The thermodynamic parameters for the formation of 2 were determined.This revised version was published online in December 2005 with corrections to the Cover Date. 相似文献
Multinuclear NMR data (13C, 31P, 13C–{31P}, 13C–{103Rh} and 31P–{103Rh}) for a series of mono- and di-substituted derivatives of Rh6(CO)16 containing neutral two electron donor ligands [Rh6(CO)15L, (L=NCMe, py, cyclooctene, PPh3, P(OPh)3,1/2(μ2,η1:η1-dppe)); Rh6(CO)14(LL), (LL=cis-CH2=CMe-CMe=CH2, dppm, dppe, (P(OPh)3)2)] are reported; these data show that the solid state structure is maintained in solution. Detailed assignments of the 13CO NMR spectra of Rh6(CO)15(PPh3) and Rh6(CO)14(dppm) clusters have been made on the basis 13C–{103Rh} double resonance measurements and the specific stereochemical features of the observed long range couplings in these clusters have been studied. The stereochemical dependence of 3J(P–C) for terminal carbonyl ligands is discussed and the values of 3J(P–C) are found to be mainly dependent on the bond angles in the P–Rh–Rh–C fragment; these data enable the fine structure of the complex multiplets in the 13C–{1H} and 31P–{1H} NMR spectra of Rh6(CO)14 (dppm) to be simulated. Variable temperature 13C–{1H} NMR measurements on Rh6(CO)15(PPh3) reveal the carbonyl ligands in this complex to be fluxional. The fluxional process involves exchange of all the CO ligands except the two terminal CO's associated with the rhodium trans to the substituted rhodium and can be explained by a simple oscillation of the PPh3 on the substituted rhodium atom aided by concomitant exchange of the unique terminal CO on this rhodium with adjacent μ3-CO's. 相似文献
UV irradiation of [Et4N] [V(CO)6] in the presence of the tripod ligands (L) MeC(CH2PPh2)3 (cp3) and P(CH2CH2PPh2)3 (pp3) yields [Et4N] [V(CO)5L], cis-[Et4N] [V(CO)4L] and mer-[Et4N] [V(CO)3L] (where the meridional configuration for L = cp3 is uncertain). Except for [Et4N] [V(CO)5cp3], all these species were isolated. The complexes are characterized by their IR, 31P and 51V NMR spectra. 相似文献
The reaction of IrH3(PPh3)2 with p-substituted aryldiazonium salts gives the compounds [IrH2(NHNC6H4R)(PPh3)2]+BF4- at low temperature (-10°C) and the o-metalated complexes [IC6H3R)(PPh3)2]+BF4- (R F, OCH3) at 40–50°C. The reactions of the o-metalated complexes with CO, PPh3, NaI and HCl have been studied. 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
Mono-cyclopentadienyl complexes CpVX2(PR3)2 and Cp′VX2 (PR3)2 (Cp = η5- C5H5; Cp′ = η5-C5H4Me; R = Me, Et; X = Cl, Br) have been prepared by reaction of VX3(PR3)2 with CpM (M = Na, T1, SnBun3, 1/2 Mg) or Cp′Na. Attempts to prepare analogous complexes with other phosphine ligands, PPh3, PPh2 Me, PPhMe2, Pcy3, DMPE and DPPE failed. Reduction of CpVCl2(PEt3)2 with zinc or aluminium under CO (1 bar) offers a simple method for the preparation of CpV(CO)3(PEt3). The crystal structure of the trimethylphosphine complex CpVCl2(PMe3)2 is reported. 相似文献
The reaction of [Ru(CO)2(PPh3)3] (1) with o-styryldiphenylphophine (SP) (2) gave [Ru(CO)2(PPh3)(SP)] (3) in 83% yield. This styrylphosphine ruthenium complex 3 can also be synthesized by the reaction of [Ru(p-MeOC6H4NN)(CO)2(PPh3)2]BF4 (4) with NaBH4 and 2 in 50% yield. When “Ru(CO)(PPh3)3” generated by the reaction of [RuH2(CO)(PPh3)3] (8) with trimethylvinylsilane reacted with 2, [Ru(CO)(PPh3)2(SP)] (10) was produced in moderate yield as an air sensitive solid. The spectral and X-ray data of these complexes revealed that the coordination geometries around the ruthenium center of both complexes corresponded to a distorted trigonal bipyramid with the olefin occupying the equatorial position and the C-C bonding in the olefin moiety in 3 and 10 contained a significant contribution from a ruthenacyclopropane limiting structure. Complexes 3 and 10 showed catalytic activity for the hydroamination of phenylacetylene 11 with aniline 12. Ruthenium complex 3 in the co-presence of NH4PF6 or H3PW12O40 proves to be a superior catalyst system for this hydroamination reaction. In the case of the reaction using H3PW12O40 as an additive, ketimines (13) was obtained in 99% yield at a ruthenium-catalyst loading of 0.1 mol%. Some aniline derivatives such as 4-methoxy, 4-trifluoromethyl-, and 4-bromoanilines can also be used in this hydroamination reaction. 相似文献
The dianion [RuIr4(CO)15]2- has been obtained by reductive carbonylation of mixtures of Ir4(CO)12 and RuCl3 · χ H2O, and the bis(triphenylphosphine)-iminium salt has been characterized by single-crystal X-ray diffraction techniques. Crystal data: [((C6H5)3P)2N]2[RuIr4(CO)15], space group P (Z 2), a 11.425(3), b 14.141(2), c 25.979(5) Å, α 84.55(1), β 83.53(2), γ 80.71(2)°. The mixed-metal cluster has a structure with an elongated trigonal bipyramidal array of metal atoms in which Ru occupies an apical position. The anion is unstable in vacuum or in an N2 atmosphere yielding predominantly another mixed-metal species which is not as yet fully characterized. Upon reexposure to CO, this latter species is converted back to [RuIr4(CO)15]2-, plus additional products. 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
