The hydridic complex HRu3(CO)9(-C2But) (Complex 1), containing an acetylide coordinated in perpendicular fashion with respect to one edge of the triangular cluster, catalyzes the hydrogenation of alkynes and of 1,4-cyclohexadiene (1,4-CHD) either under homogeneous and under solid–gas conditions. Cluster catalysis is likely to occur; however, under homogeneous conditions, evidence for partial fragmentation of the cluster has also been found. In these conditions, formation of known metallacyclic compounds and of the new dinuclear derivative Ru2(CO)6 (HC2But)(C2Ph2) (Complex 2a) has been observed: they are presumably inactive byproducts. 相似文献
The synthesis, IR spectra, and the temperatures of the transition into a ferromagnetic state (Tc) of layered ferromagnetics [R3RX[MCr(C2O4)3 (M = Mn, Fe, Co, Cu, and Ni) with the [Ph3BuP]+, [Bu3RN]+ (R = Pr, Et, and Me) cations capable of subsequently changing the distances between metallooxalate layers have been considered. The temperatureTc has been found to be independent of the size of the organic cation. It is believed that the determining factors in the transition to a ferromagnetic state are exchange interactions inside the metallooxalate layer.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 2327–2330, September, 1996. 相似文献
Equimolar quantities of [Mo (CO) (η2-RC2R′)2Cp] [BF4] (R=R′=Me Ph R=Me R′=Ph) and L L′ or L″ {L L′ or L″= [WI2 (CO){PhP(CH2CH2PPh2)2-PP′} (η2-RC2R′)]} (L R=R′=Me L′ R=R′=Ph L″ R=Me R′=Ph) react in CH2Cl2 at room temperature to give the new bimetallic complexes[Mo (CO) (L L′ or L″–P) (η2-RC2R′)Cp] [BF4] (1–9) via displacement of the alkyne ligand on the molybdenum centre The complexes have been characterised by elemental analysis IR and 1 H NMR spectroscopy and in selected cases by 31 P NMR spectroscopy. 相似文献
The new [Pt(5)(CO)(5){Cl(2)Sn(μ-OR)SnCl(2)}(3)](3-) (R = H, Me, Et, (i)Pr; 1-4) clusters contain trigonal bipyramidal (TBP) Pt(5)(CO)(5) cores, as certified by the X-ray structures of [Na(CH(3)CN)(5)][NBu(4)](2)[1]·2CH(3)CN and [PPh(4)](3)[4]·3CH(3)COCH(3). The TBP geometry, which is rare for group 10 metals, is supported by an unprecedented interpenetration with a nonbonded trigonal prism of tin atoms. By capping all the Pt(3) faces, the Sn(II) lone pairs account for both Sn-Pt and Pt-Pt bonding, as indicated by DFT and topological wave function studies. In the TBP interactions, the metals use their vacant s and p orbitals using the electrons provided by Sn atoms, hence mimicking the electronic picture of main group analogues, which obey the Wade's rule. Other metal TBP clusters with the same total electron count (TEC) of 72 are different because the skeletal bonding is largely contributed by d-d interactions (e.g., [Os(5)(CO)(14)(PR(3))(μ-H)(n)](n-2), n = 0, 1, 2). In 1-4, fully occupied d shells at the Pt(ax) atoms exert a residual nucleophilicity toward the adjacent main group Sn(II) ions permitting their hypervalency through unsual metal donation. 相似文献
Russian Chemical Bulletin - Gold complexes [Ph3PR]+[Au(CN)2I2-trans]?, where R = Et (1), CH2Ph (2), Ph (3), were synthesized by the reaction of potassium dicyanodiiodoaurate with... 相似文献
The first examples of polymeric homoleptic iron chalcogenolato complexes (1)(∞)[Fe(SePh)(2)] and (1)(∞)[Fe(SeMes)(2)] (Ph = phenyl = C(6)H(5), Mes = mesityl = C(6)H(2)-2,4,6-(CH(3))(3)) have been both prepared by reaction of [Fe(N(SiMe(3))(2))(2)] with two equivalents of HSeR (R = Ph, Mes) while (1)(∞)[Fe(SePh)(2)] was found to be also easily accessible through reactions of either FeCl(2), Fe(OOCCH(3))(2) or FeCl(3) with PhSeSiMe(3) in THF. In the crystal, the two compounds form one-dimensional chains with bridging selenolate ligands comprising distinctly different Fe-Se-Fe bridging angles, namely 71.15-72.57° in (1)(∞)[Fe(SePh)(2)] and 91.80° in (1)(∞)[Fe(SeMes)(2)]. Magnetic measurements supported by DFT calculations reveal that this geometrical change has a pronounced influence on the antiferromagnetic exchange interactions of the unpaired electrons along the chains in the two different compounds with a calculated magnetic exchange coupling constant of J = -137 cm(-1) in (1)(∞)[Fe(SePh)(2)] and J = -20 cm(-1) in (1)(∞)[Fe(SeMes)(2)]. In addition we were able to show that the ring molecule [Fe(SePh)(2)](12) which is a structural isomer of (1)(∞)[Fe(SePh)(2)] behaves magnetically similar to the latter one. Investigations by powder XRD reveal that the ring molecule is only a metastable intermediate which converts in THF completely to form (1)(∞)[Fe(SePh)(2)]. Thermal gravimetric analysis of (1)(∞)[Fe(SePh)(2)] under vacuum conditions shows that the compound is thermally labile and already starts to decompose above 30 °C in a two step process under cleavage of SePh(2) to finally form at 250 °C tetragonal PbO-type FeSe. The reaction of (1)(∞)[Fe(SePh)(2)] with the Lewis base 1,10-phenanthroline yielded, depending on the conditions, the octahedral monomeric complexes [Fe(SePh)(2)(1,10-phen)(2)] and [Fe(1,10-phen)(3)][Fe(SePh)(4)]. 相似文献
The behavior of [Fe(2) (CO)(4) (κ(2) -PNP(R) )(μ-pdt)] (PNP(R) =(Ph(2) PCH(2) )(2) NR, R=Me (1), Ph (2); pdt=S(CH(2) )(3) S) in the presence of acids is investigated experimentally and theoretically (using density functional theory) in order to determine the mechanisms of the proton reduction steps supported by these complexes, and to assess the role of the PNP(R) appended base in these processes for different redox states of the metal centers. The nature of the R substituent of the nitrogen base does not substantially affect the course of the protonation of the neutral complex by CF(3) SO(3) H or CH(3) SO(3) H; the cation with a bridging hydride ligand, 1?μH(+) (R=Me) or 2?μH(+) (R=Ph) is obtained rapidly. Only 1?μH(+) can be protonated at the nitrogen atom of the PNP chelate by HBF(4) ?Et(2) O or CF(3) SO(3) H, which results in a positive shift of the proton reduction by approximately 0.15?V. The theoretical study demonstrates that in this process, dihydrogen can be released from a η(2) -H(2) species in the Fe(I) Fe(II) state. When R=Ph, the bridging hydride cation 2?μH(+) cannot be protonated at the amine function by HBF(4) ?Et(2) O or CF(3) SO(3) H, and protonation at the N atom of the one-electron reduced analogue is also less favored than that of a S atom of the partially de-coordinated dithiolate bridge. In this situation, proton reduction occurs at the potential of the bridging hydride cation, 2?μH(+) . The rate constants of the overall proton reduction processes are small for both complexes 1 and 2 (k(obs) ≈4-7?s(-1) ) because of the slow intramolecular proton migration and H(2) release steps identified by the theoretical study. 相似文献
The acetone complex [Fe(CO)2(Me2CO)(η5-C5H5)][PF6] reacts with L (L = H2NNHCSNH2, cy-C5H10CNNHCSNH2, or R′R″CNNHCSNH2 where R′ = R″ = Me; R′ = H, R″ = Ph; R′ = H, R″ = p-NO2Ph; R′ = p-MePh) in refluxing trichloromethane to give the new complexes [Fe(CO)2L(η5-C5H5)][PF6]. The complexes are clearly coordinated through the sulphur atom since the thiosemicarbazide complex reacts with benzaldehyde to afford the corresponding thiosemicarbazone compound. 相似文献
The photochemistry of the tris-substituted clusters Ru3(CO)9(PR3)3 (R=Ph or OMe) with no added ligands, with CO, C2H4, alkynes and H2 is compared and contrasted with results obtained for analogous thermal reactions. Photolysis of a CH2Cl2 solution of Ru3(CO)9(PPh3)3 leads to the metallated complex HRu3(CO)8(PPh3)2(PPh2C6H4). In CCl4, Ru(CO)3(PR3)Cl2 is formed on photolysis of Ru3(CO)9(PR3)3. Photolysis of CO saturated solutions of Ru3(CO)9(PR3)3 leads to Ru(CO)4(PR3). C2H4 saturated solutions of Ru3(CO)9(PR3)3 generate the novel Ru(CO)3(PR3)(2-C2H4) complexes upon photolysis. With C2H2, photolysis of solutions of Ru3(CO)9(PR3)3 leads to the novel complexes Ru(CO)3(PR3)(2-C2H2). Substituted alkyne complexes have been prepared. Thermolysis of Ru3(CO)9(PR3)3 with HCCPh leads to the novel acetylide clusters HRu3(CO)6(PR3)3(3-2-C2Ph). With PhC CPh, only Ru3(CO)9{P(OMe)3}3 reacts, yielding the novel alkyne cluster Ru3(CO)6{P(OMe)3}3(3-2-C2Ph2). With H2, photolysis of CH2Cl2 solutions of Ru3(CO)9(PR3)3 leads to H2Ru(CO)2(PR3)2. Irradiating a 4:1 CH2Cl2 to EtOAc solution of Ru3(CO)9(PR3)3 under an atmosphere of H2 leads to the novel dihydrido species H2Ru3(CO)7(PR3)3. Thermolysis of H2 saturated solutions of Ru3(CO)9(PR3)3 leads to H4Ru4(CO)8(PR3)4. 相似文献
The photo-induced decarbonylation of CpCr(NO)(CO)2(1a) in MeCN solution in the presence of R2E2 (E = S, Se; R = Me, Ph) leads to the formation of chalcogenolato-bridged binuclear complexes Cp2Cr2(NO)2(-ER)2 [E = S; R = Me (2a), Ph (3a); E = Se, R = Me (4a), Ph (5a)] while reactions between CpM(NO)(CO)2 [M = Mo (1b), W (1c)] and Ph2E2 (E = S, Se) result in mononuclear complexes CpM(NO)(EPh)2 [M = Mo; E = S (9b), Se (10b); M = W, E = S (11c), Se (12c)]. The corresponding reactions of (1b) with Me2E2 (E = S, Se) yielded both mono and binuclear complexes: CpMo(NO)(SeMe)2(8b), Cp2Mo2(NO)2(-EMe)2 [E = S (6b), Se (7b)]. The new complexes have been characterized by i.r., 1H-, 13C-n.m.r. spectra and by electron-impact mass spectrometry. 相似文献
The diiron ynamine complex [Fe2(CO)7{-C(Ph)C(NEt2)}] (1) reacts with the diphenylbuta-1, 4-diyne, PhCC-CCPh, in refluxing hexane to yield three isomer complexes [Fe2(CO)6{C(Ph)C(NEt2)C(Ph)C(C2Ph}] (2a), [Fe2(CO)6{C(Ph)C(NEt2)C(C2Ph)C(Ph)}] (2b), and [Fe2(CO)6{NEt2)C(Ph)C(C2)C(Ph)}] (2c) All three compounds were identified by their1H NMR spectra. Compounds2a and2c were characterized by single crystal X-ray diffraction analyses. Crystal data: for2a: space group = P21/n,a = 17.873(1) Å, = 18.388(6) Å,c = 9.429(3) Å = 91.99(3)°,Z = 4.3751 reflections,R = 0.044; for2c: space group = P21/n,a = 40.58(2) å,b = 12.101(9) Å,c = 12.551(5) Å, = 94.29(7)°,Z = 8.4723 reflection,R = 0.076. Complexes2a and2b result from a [2 + 2] cycloaddition between one of the CC triple bonds of the diyne ligand and the FeC carbene bond, whereas2c results from insertion of one of the CC group into the bridging carbene. Addition of [Fe2(CO)9] on2a gave two major products, the tripledecker [Fe3(CO)8{C(Ph)C(NEt2)C(C2Ph)}], (3 and a tetrairon cluster [Fe4(CO)11{C(Ph)C(NEt2)C(Ph)C(C2Ph)}] (4). Both compounds were characterized by single crystal diffraction analyses. Crystal data: for3: space group = P21/n,a = 12.039(3) Å,b = 18.046(3) å,c = 15.270(2) Å, = 90.11(2)°,Z = 4, 1430 reflections,R = 0.067; for4 space group = C2/c,a = 18.633(3) Å,b = 21.467(1)_Å,c = 20.742(2) Å, = 115.03(8)°,Z = 8.992 reflections, R = 0.076. Complex4 is based on a spiked triangular cluster with the alkynyl triple bond attached in
3-parallel mode on the triangular grouping. 相似文献
The synthesis of new cyclometalated compounds of palladium(II) with the mixed-donor bidentate ligands o-Ph2PC6H4–CH=NR is described. Two series of complexes [Pd(C^N)(o-Ph2PC6H4–CH=NR)][PF6] have been prepared using either azobenzene or 2-phenylpyridine as cyclometalated ligands [C^N=azobenzene (azb); R=Me (1a), Et (2a), nPr (3a), iPr (4a), tBu (5a), Ph (6a), NH–Me (7a); C^N=2-phenylpyridine (phpy); R=Me (1b), Et (2b), nPr (3b), iPr (4b), tBu (5b), Ph (6b), NH–Me (7b)]. The new complexes were characterized by partial elemental analyses and spectroscopic methods (IR, FAB, 1H and 31P NMR). The molecular structures of compounds 2a (monoclinic, P 21/n) and 1b (monoclinic, C 2/c) have been determined by a single-crystal diffraction study. In both cases this technique revealed the relative trans configuration between the phosphorus atom and the nitrogen atom of the ortho-metalated ligand. 相似文献
Abstract The dinuclear palladium diselenolenes [Pd2(Se2CnH2n?4)2(PR3)2] react with haloalkanes, via electrophilic attack at the bridging selenium atoms, to yield the neutral mononuclear square planar palladium(II) complexes [PdX(Se{R′}CnH2n?4Se)(PR3)] (n = 6, 7, 8; R = Ph, Bu; X = Br, I; R′ = Me, Et, etc.), containing a novel chelating selenolato/selenide ligand, in which the alkylated selenium and halogen donor atoms occupy cis-positions. The products have been characterised by mass spectrometry and multinuclear NMR spectroscopy; the molecular structure of the compound with n = 8, R = Ph, R′ = Et has been determined by X-ray crystallography. 相似文献
The μ-acyl complex B″O (I) reacts with PMe2Ph to yield the allenyl-substituted μ-carbyne complex HOs3(CO)10{μ-CC(Ph)CC(Ph)Re(CO)4PMe2Ph} (II). Complex II has been characterized by an X-ray structural study. 相似文献
Reactions of the alkyne cluster Os3(μ-CO)(CO)9(μ3-Me3C2Me) with alkynes Me3SiC≡CR (R=Me, Bun) in refluxing hexane result in the formation of clusters Os3(CO)9{μ3-C(SiMe3)=C(Me)C=C(SiMe3)=C(Me)C=C(SiMe3)R} (2a: R=Me;3a: R=Bun). The dienediyl ligand in these complexes is formed by alkyne-vinylidene coupling, with vinylidene generated in the course of reaction from the alkyne molecule by the acetylene-vinylidene rearrangement involving a 1,2-shift of the Me3Si group. The structure of cluster3a was determined by X-ray structural analysis. The dienediyl ligand is coordinated to three metal atoms of the cluster framework by two π-ethylene bonds with two osmium atoms and two σ-bonds with the third osmium atom with the formation of the osmacyclobutene moiety. The1H and13C NMR study of13CO-enriched samples of clusters2a and3a revealed the stereochemical nonrigidity of these molecules due to the exchange of the hydrocarbon and carbonyl ligands. 相似文献