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1.
2.
Treatment of [Ru3(CO)9{P(C4H3S)3}(μ-dppm)] (1) [dppm = bis(diphenylphosphino)methane] with molecular oxygen in benzene at 60 °C affords oxo-capped [Ru3(CO)63-CO){P(C4H3S)3}(μ-dppm)(μ3-O)] (2), while with elemental sulfur and selenium related chalcogenide-capped clusters [Ru3(CO)63-CO){P(C4H3S)3}(μ-dppm)(μ3-E)] (3, E = S; 5, E = Se) and bis(chalcogenide) clusters [Ru3(CO)6{P(C4H3S)3}(μ-dppm)(μ3-E)2] (4, E = S; 6, E = Se) result. Reaction of 1 with H2S in refluxing THF affords the previously reported [(μ-H)2Ru3(CO)7(μ-dppm)(μ3-S)] (7) together with the new sulfido-capped dihydride [(μ-H)2Ru3(CO)6{P(C4H3S)3}(μ-dppm)(μ3-S)] (8). All new compounds have been characterized by spectroscopic data, and 2 and 8 by single-crystal X-ray diffraction analyses. Oxo-capped 2 consists of a triangular ruthenium framework capped on opposite sides by oxo and carbonyl groups, while 8 consists of a ruthenium triangle by a capping sulfido ligand and two inequivalent bridging hydride ligands.  相似文献   

3.
Reactions of [Pt2(μ-S)2(PPh3)4] with the diarylthallium(III) bromides Ar2TlBr [Ar = Ph and p-ClC6H4] in methanol gave good yields of the thallium(III) adducts [Pt2(μ-S)2(PPh3)4TlAr2]+, isolated as their salts. The corresponding selenide complex [Pt2(μ-Se)2(PPh3)4TlPh2]BPh4 was similarly synthesised from [Pt2(μ-Se)2(PPh3)4], Ph2TlBr and NaBPh4. The reaction of [Pt2(μ-S)2(PPh3)4] with PhTlBr2 gave [Pt2(μ-S)2(PPh3)4TlBrPh]+, while reaction with TlBr3 gave the dibromothallium(III) adduct [Pt2(μ-S)2(PPh3)4TlBr2]+[TlBr4]. The latter complex is a rare example of a thallium(III) dihalide complex stabilised solely by sulfur donor ligands. X-ray crystal structure determinations on the complexes [Pt2(μ-S)2(PPh3)4TlPh2]BPh4, [Pt2(μ-S)2(PPh3)4TlBrPh]BPh4 and [Pt2(μ-S)2(PPh3)4TlBr2][TlBr4] reveal a greater interaction between the thallium(III) centre and the two sulfide ligands on stepwise replacement of Ph by Br, as indicated by shorter Tl-S and Pt?Tl distances, and an increasing S-Tl-S bond angle. Investigations of the ESI MS fragmentation behaviour of the thallium(III) complexes are reported.  相似文献   

4.
The cationic carbyne complex [Cp(CO)2MnCC6H5]BBr4 (1) reacts with PPN[Rh(CO)4] (2) to give the title cluster [(μ3-CC6H5)(μ-CC6H5) Rh2Mn2Cp2(μ-CO)3(CO)3] (3) whose structure has been determined by X-ray diffraction. The electrochemical properties of 3 have been investigated using cyclic voltammetric method. At 60 °C and 2.0 MPa of initial total CO/H2 (1:1) pressure, the catalytic activity of 3 towards hydroformylation of styrene has also been checked.  相似文献   

5.
A new polynuclear copper (II) complex, derived from the azido-bridging ligand and 2-aminopyrimidine, has been synthesized and its 3-D structure has been determined by X-ray diffraction methods at two different temperatures. The compound crystallizes in the triclinic system space group, with the central copper atom lying on an inversion centre. The crystal structure is built up by trinuclear units (each of them contains two double end-on azido bridges) linked through two azide ions in an end-to-end (EE) fashion, to yield the polymer chain [Cu3(ampym)21,1-N3)41,3-N3)2(dmf)2]n. Magnetic susceptibility measurement shows a ferromagnetic interaction above 30 K, whereas a weak anti-ferromagnetic interaction prevails in the range of 30-2 K.  相似文献   

6.
Routes to the synthesis of the mixed sulfide-phenylthiolate complex [Pt2(μ-S)(μ-SPh)(PPh3)4]+ have been explored; reaction of [Pt2(μ-S)2(PPh3)4] with excess Ph2IBr proceeds readily to selectively produce this complex, which was structurally characterised as its PF6 salt. Reactions of [Pt2(μ-S)2(PPh3)4] with other potent arylating reagents (1-chloro-2,4-dinitrobenzene and 1,5-difluoro-2,4-dinitrobenzene) also produce the corresponding nitroaryl-thiolate complexes [Pt2(μ-S){μ-SC6H2(NO2)2X}(PPh3)4]+ (X = H, F). The complex [Pt2(μ-S)(μ-SPh)(PPh3)4]+ reacts with Me2SO4 to produce the mixed alkyl/aryl bis-thiolate complex [Pt2(μ-SMe)(μ-SPh)(PPh3)4]2+, but corresponding reactions with the nitroaryl-thiolate complexes are plagued by elimination of the nitroaryl group and formation of [Pt2(μ-SMe)2(PPh3)4]2+. [Pt2(μ-S)(μ-SPh)(PPh3)4]+ also reacts with Ph3PAuCl to give [Pt2(μ-SAuPPh3)(μ-SPh)(PPh3)4]2+.  相似文献   

7.
The reaction between [Fe2Ir2(CO)12]2− and diphenylacetylene in refluxing CH3CN yields the substituted cluster [Fe2Ir2(CO)10(PhC2Ph)]2− (1). In the crystals, the four metal atoms define a butterfly arrangement whose Ir-Ir hinge is parallel to the acetylenic C2 unit. The neutral triangular cluster [FeIr2(CO)9(PhC2Ph)] (2) is obtained by the treatment of 1 with acids at room temperature; in this 48 valence electrons species, the C-C and the Ir-Ir bonds are also parallel, in the coordination mode.The cluster [Fe2Rh(CO)10] reacts with diphenylacetylene in refluxing THF yielding [Fe2Rh(CO)8(PhC2Ph)] (3). In this 46 C.V.E.’s cluster, the C2 unit is perpendicular to the Fe-Fe edge, exemplifying the bonding mode. According to 13C NMR spectra, the structure of the three clusters is maintained in solution. Electrochemical investigations show that the one-electron oxidation of [Fe2Ir2(CO)10(L)]2− (L = 2CO, PhC2Ph) as well as the one-electron reduction of [Fe2Rh(CO)8(PhC2Ph)] only generates the respective short lived products.  相似文献   

8.
Reaction of [Pt2(μ-S)2(PPh3)4] with a number of transition metal-iodo complexes leads to the formation of the cationic iodo analogue [Pt2(μ-S)(μ-I)(PPh3)4]+, identified using electrospray ionisation mass spectrometry (ESI MS). Synthetic routes to this complex were developed, using the reaction of [Pt2(μ-S)2(PPh3)4] with either [PtI2(PPh3)2] or elemental iodine. The complex was characterised by NMR spectroscopy, ESI MS and an X-ray structure determination, which reveals the presence of a planar, disordered {Pt2SI}+ core. Monitoring the iodine reaction by ESI MS allows the identification of various iodine species, including the short-lived intermediate [Pt2(μ-S)2(PPh3)4I]+, which allows a mechanism for the reaction to be proposed.  相似文献   

9.
The 86-electron dicationic octahedral rhodium clusters containing Cp (Cp = C5H5) ligands and either an interstitial carbon atom, [Rh6Cp66-C)]2+ ([1]2+), or two carbonyl groups, [Rh6Cp63-CO)2]2+ ([2]2+), were synthesized in low yields by reactions of Rh3Cp3(μ-CO)3 with RhCp(C2H4)2 or [RuCp(MeCN)3]+ (Cp = C5Me5), respectively. The structures of [1]2+ and [2]2+ were determined by X-ray diffraction. Their electrochemical behavior proved that they possess a rather extended electron transfer activity. In accordance with DFT calculations, the nearly octahedral structure of [1]2+ and [2]2+ is retained both upon oxidation (2+/3+) and the first reduction (2+/+); however, the second reduction (+/0) results in the breaking of one (for [1]0) or two (for [2]0) Rh-Rh bonds. In the case of the related Dahl’s nickel cluster Ni6Cp6 the nearly octahedral structure is retained upon all redox steps (3+/2+/+/0/−/2−).  相似文献   

10.
Reaction of the metalloligand [Pt2(μ-S)2(PPh3)4] with the N-heterocyclic carbene (NHC) complexes IPrAuCl, IMesAuCl and IMesAgCl in methanol gave the first examples of metal adducts of [Pt2(μ-S)2(PPh3)4] that contain NHC ligands, namely [Pt2(μ-S)2(PPh3)4AuL]+ (L = IPr, IMes) and [Pt2(μ-S)2(PPh3)4AgIMes]+. The complexes were isolated as hexafluorophosphate salts. Reaction of [Pt2(μ-S)2(PPh3)4] with excess IPrAuCl in refluxing methanol yielded only the mono-adduct, in contrast to the behaviour with the gold(I) phosphine complex Ph3PAuCl, which undergoes double addition giving [Pt2(μ-SAuPPh3)2(PPh3)4]2+. The X-ray structure of [Pt2(μ-S)2(PPh3)4AuIPr]PF6 was determined and reveals that the ‘free’ sulfide is substantially sterically protected by the IPr ligand, accounting for the low reactivity towards addition of a second AgIPr+ moiety.  相似文献   

11.
The reactions of [Pt2(μ-S)2(PPh3)4] towards a range of palladium(II) complexes containing organometallic ligands (cyclopalladated N-donor ligands, η3-allyl, phenyl) have been explored, leading to the formation of a series of cationic, trinuclear sulfido-bridged aggregates containing {Pt2PdS2} cores. [Pt2(μ-S)2(PPh3)4] also reacts with the platinum(II) hydride complex trans-[PtHCl(PPh3)2] giving the adduct [Pt2(μ-S)2(PPh3)4PtH(PPh3)]+. X-ray crystal structure determinations on the complexes [Pt2(μ-S)2(PPh3)4PdPh(PPh3)]PF6 and [Pt2(μ-S)2(PPh3)4PtH(PPh3)]PF6 are reported, and show the expected bis μ3-sulfido aggregates with three square-planar metal centres.  相似文献   

12.
Two novel tetranuclear compounds with an unprecedented mode of a hydrogenphosphato bridge, [Cu4(dpyam)443-HPO4)2(μ-X)2]2+ (in which dpyam = di-2-pyridylamine and X = Cl (1), Br (2)) have been synthesised and characterised structurally and magnetically. The Cu(II) ions in the structures each display a square-pyramidal geometry, with two tridentate hydrogenphosphato groups bridging four copper atoms in a μ43 coordination mode which is rarely found in hydrogenphosphate metal compounds. Each (different) pair of Cu(II) ions is additionally bridged by halide ions, with relatively long Cu-X distances (2.551(3)-2.604(3) Å for 1 and 2.707(1)-2.766(2) Å for 2) and subsequently also a small Cu-X-Cu angle (65.7(1)° and 65.1(1)° for 1 and 61.6(1)° and 62.4(1) for 2) and a large Cu-X-Cu angle (95.5(1)° and 96.5(1)° for 1 and 91.1(1)° and 92.6(1)° for 2). Cu?Cu distances in the tetranuclear units varies from 2.802(3) to 5.232(3) Å for 1 and from 2.834(1) to5.233(1) Å in 2. The lattice structures are stabilised by extensive intermolecular hydrogen bonds. The magnetic susceptibility measurements down to 5 K revealed a weak ferromagnetic interaction between the outer pairs of Cu(II) ions which vary from 22 to 46 cm−1 in 1 and 12 to 33 cm−1 in 2 and a moderately strong antiferromagnetic interaction between the inner Cu(II) ions of −79 cm−1 in 1 and −83 cm−1 in 2, via the Cu-O-P-O-Cu pathway.  相似文献   

13.
The metalloligand [Pt2(μ-S)2(PPh3)4] reacts with Bi(S2CNEt2)3 or Bi(S2COEt)3 in methanol to produce the orange cationic adducts [Pt2(μ-S)2(PPh3)4Bi(S2CNEt2)2]+ and [Pt2(μ-S)2(PPh3)4Bi(S2COEt)2]+, respectively, isolated as their hexafluorophosphate salts. An X-ray structure determination on [Pt2(μ-S)2(PPh3)4Bi(S2CNEt2)2]PF6 reveals the presence of a six-coordinated bismuth centre with an approximately nido-pentagonal bipyramidal coordination geometry. Fragmentation pathways for both complexes have been probed using electrospray ionisation mass spectrometry; ions [Pt2(μ-S)2(PPh3)2Bi(S2CXEtn)2]+ (X = O, n = 1, X = N, n = 2) are formed by selective loss of two PPh3 ligands, and at higher cone voltages the species [(Ph3P)PtS2Bi]+ is observed. Ions formed by loss of CS2 are also observed for the xanthate but not the dithiocarbamate ions.  相似文献   

14.
Reaction of [WVIS4]2− with ethane-1,2-dithiol edtH2 in the presence of the sulfide scavenger Cd2+ yielded the dinuclear tungstate syn-[{(edt)WV(O/S)}2(μ-S)2]2− (1), with the terminal S/O disordered over the two tungsten sites in the ratio 0.8:02. In the presence of thiocyanate, phosphine and CuI, the anionic cuboidal clusters of composition [{(SCN)3WV}2{CuI(PPh3)}23-S)4]2− (2) and (3, diphos = 1,2-bis(o-diphenylphosphinophenyl)ethane), and possibly via an intermediate [{(SCN)3WVS}2(μ-S)2]4−. The crystal and molecular structures of [Et4N]21, [Et4N]22 · H2O and [Et4N]23 · H2O have been determined.  相似文献   

15.
The SS bond-activation of diorganyl disulfide by the anionic metal carbonyl fragment [Mn(CO)5] gives rise to an extensive chemistry. Oxidative decarbonylation addition of 2,2′-dithiobis(pyridine-N-oxide) to [Mn(CO)5], followed by chelation and metal-center oxidation, led to the formation of [MnII(SC5H4NO)3] (1). The effective magnetic moment in solid state by SQUID magnetometer was 5.88 μB for complex 1, which is consistent with the MnII having a high-spin d5 electronic configuration in an octahedral ligand field. The average Mn(II)S, SC and NO bond lengths of 2.581(1), 1.692(4) and 1.326(4) Å, respectively, indicate that the negative charge of the bidentate 1-oxo-2-thiopyridinato [SC5H4NO] ligand in complex 1 is mainly localized on the oxygen atom. The results are consistent with thiolate-donor [SC5H4NO] stabilization of the lower oxidation state of manganese (Mn(I)), while the O,S-chelating [SC5H4NO] ligand enhances the stability of manganese in the higher oxidation state (Mn(II)). Activation of SS bond as well as OH bond of 2,2′-dithiosalicylic acid by [Mn(CO)5] yielded [(CO)3Mn(μ-SC6H4C(O)O)2Mn(CO)3]2− (4). Oxidative addition of bis(o-benzamidophenyl) disulfide to [Mn(CO)5] resulted in the formation of cis-[Mn(CO)4(SR)2] (R=C6H4NHCOPh) which was employed as a chelating metallo ligand to synthesize heterotrinuclear [(CO)3Mn(μ-SR)3Co(μ-SR)3Mn(CO)3] (8) possessing a homoleptic hexathiolatocobalt(III) core.  相似文献   

16.
Reaction of [Pt2(μ-S)2(PPh3)4] with a range of zinc(II) and cobalt(II) complexes ML2, where L is a β-diketonate ligand CH3COCHCOCH3, PhCOCHCOPh, CF3COCHCOTh (Th = 2-thienyl)] permits the synthesis of adducts [Pt2(μ-S)2(PPh3)4M(diketonate)]+, isolated as their salts in moderate yields. The cobalt and zinc acetylacetonate complexes were characterised by single-crystal X-ray diffraction studies, which reveal isomorphous structures, with tetrahedral heterometal centres.  相似文献   

17.
Three Mn(III,III) complexes containing dibenzoylmethane (dbm), Mn2(OMe)2(dbm)2(ClH2CCOO)2 (1), Mn2(OMe)2(dbm)2(Cl2HCCOO)2 (2) and Mn2(OMe)2(dbm)2(Cl3CCOO)2 (3) were synthesized. Crystal structure determination and magnetic characterization were done for 2. The Mn?Mn distance in complex 2 is 2.865 Å. It exhibits antiferromagnetic coupling with exchange parameter |J| = 20.4 cm−1 (H = −2JSASB). All three complexes, though insoluble in common solvents, catalyse the disproportionation of hydrogen peroxide when dispersed on silica gel with turnover numbers ∼150-300. DFT simulations showed that bridging moieties have remarkable effect on intermetallic distances in dimanganese(III,III) complexes.  相似文献   

18.
The reactions of the triangulo-cluster [Pt3(μ-CO)3(PtBu3)3] with activated olefins and alkynes have been examined under various conditions. At low temperature, cluster fragmentation occurs yielding the Pt(0) complexes [Pt(CO)(PtBu3)(olefin)] (olefin = maleic anhydride and maleimide), while di(tert-butyl)acetylenedicarboxilate reacts quantitatively giving the dinuclear Pt(0) complex [Pt2(CO)2(PtBu3)2(μ-η22-tBuO2CCCCO2tBu)]. At higher temperature and in the presence of alkyne in large excess, the latter dimer converts quantitatively to the monomers [Pt(CO)(PtBu3)(alkyne)] (alkyne = CF3CCCF3 and tBuO2CCCCO2tBu). The stereochemistry of these complexes has been established by NMR and IR measurements. The structure of [Pt(CO)(PtBu3)(CF3CCCF3)] was confirmed by X-ray diffraction analysis.  相似文献   

19.
The reduction of ethanolic solutions of niobium pentachloride with zinc, followed by treatment with aqueous acids serves as a versatile entry into the aqueous solution chemistry of niobium. From the zinc-reduced solution, the major intermediate, Nb42-O)22-OC2H5)4Cl4(OC2H5)4(HOC2H5)4, was isolated and the crystal structure determined by X-ray crystallography. The complex crystallizes in the orthorhombic space group Pccn, with Z=4, a=21.0105(9), b=11.0387(5), c=19.1389(8), V=4438.9(3) Å3, Mr=1090.19,R1=0.0327 and wR2=0.0876. The structure revealed a centrosymmetric tetrameric Nb(IV) complex, consisting of a pair of edge-sharing bi-octahedral Nb22-OC2H5)4Cl2(OC2H5)2(HOC2H5)2 units that are joined by two axial oxo ligands. The Nb-Nb distance of 2.7458(3) Å is consistent with a single metal-metal bond.  相似文献   

20.
[Pt5(μ-CO)5(CO)L4] (L = PPh31, PPh2Bz 2, AsPh33, PEt34, PCy35) have been synthesized by reacting [Pt3(μ-CO)3(PR3)3] with H2O2 (1 and 2), by reduction of cis-[PtCl2(CO)(PEt3)] with Zn dust (4), and by the Zn reduction of [Pt3(μ-CO)3(PCy3)3] in the presence of [PtCl2(CH3CN)2] (5). Complex 5 has not been observed previously and has been characterized by X-ray crystallography. Oxidation of the phosphine ligands with H2O2 is a new way to synthesize 1 and 2. The first complete NMR characterization of these complexes has also been achieved, and showed that these pentanuclear cluster complexes exhibit similar stereochemistries in solution and in the solid state. The observed 1JPt-Pt values do not have any correlation with the corresponding bond lengths, again pointing out the irregular behaviour of such parameter in Pt complexes.  相似文献   

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