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1.
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
2.
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
3.
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, Nb4(μ2-O)2(μ2-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 Nb2(μ2-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
4.
Yufei Song Manuel Quesada Ilpo Mutikainen Jan Reedijk 《Inorganica chimica acta》2005,358(4):1171-1178
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)2(μ1,1-N3)4(μ1,3-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
5.
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
6.
7.
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)6(μ3-CO){P(C4H3S)3}(μ-dppm)(μ3-O)] (2), while with elemental sulfur and selenium related chalcogenide-capped clusters [Ru3(CO)6(μ3-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
8.
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)}2(μ3-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
9.
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
10.
Addition of trifluoroacetic acid to syn-[MoO(μ-N-o-tol)(S2CNEt2)]2 in chloroform affords tetranuclear [{Mo2O(S2CNEt2)(η1-O2CCF3)(μ-N-o-tol)2}2(μ-O)(μ-O2CCF3)2] which has been crystallographically characterised. It consists of four molybdenum(V) centres linked via bridging imido, trifluoroacetate and oxo ligands and results from replacement of a dithiocarbamate by two trifluoroacetate ligands. 相似文献
11.
《Inorganica chimica acta》2004,357(2):571-580
Treatment of the ligand N-(2-mercaptoethyl)-3,5-dimethylpyrazole with [Pd(CH3COO)2]3 and reaction of [PdCl(μ-med)]2 with pyridine (py) or triphenylphosphine (PPh3) in the presence of AgBF4 produced the following complexes: [Pd(CH3COO)(μ-med)]2, [Pd(μ-med)(py)]2(BF4)2 and [Pd(μ-med)(PPh3)]2(BF4)2. Similar reactions carried out with 2,2′-bipyridine (bpy) or 1,3-bis(diphenylphosphino)propane (dppp) produced [Pd(μ-med)(bpy)]x(BF4)x (x=1 or 2) and [Pd(μ-med)(dppp)]x(BF4)x (x=1 or 2). Treatment of [Pd(μ-med)(bpy)]x(BF4)x with [PdCl2(CH3CN)2] produced [Pd3Cl2(μ-med)2(bpy)2](BF4)2. Treatment of [Pd(μ-med)(dppp)]x(BF4)x with [PdCl2(CH3CN)2] produced a mixture of [Pd(μ-Cl)(dppp)]2(BF4)2 and [Pd(μ-med)2(dppp)]2+. X-ray crystal structures of [Pd(μ-med)(PPh3)]2(BF4)2 · 2CH3CN and [Pd(μ-med)(bpy)]2(BF4)2 · 0.5CH3OH are presented. 相似文献
12.
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
13.
Sujittra Youngme Pongthipun Phuengphai Gerard A. van Albada Jan Reedijk 《Inorganica chimica acta》2005,358(7):2262-2268
Two novel tetranuclear compounds with an unprecedented mode of a hydrogenphosphato bridge, [Cu4(dpyam)4(μ4,η3-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 μ4,η3 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
14.
Mathieu Auzias 《Inorganica chimica acta》2006,359(10):3412-3416
The thermal reaction of Ru3(CO)12 with the biologically active acids acetyl salicylic acid (Aspirin), α-methyl-4-(isobutyl)phenylacetic acid (Ibuprofen) and 3α,7α,12α-trihydroxy-5β-cholanic acid (cholic acid) in refluxing tetrahydrofuran, followed by addition of triphenylphosphine, gives the dinuclear complexes Ru2(CO)4(OOCR)2(PPh3)2 (1: R = C6H4-2-OCOMe, 2: R = CHMe-C6H4-4-Bui, 3: C23H39O3). The single-crystal structural analysis of 1 and 2 reveals a dinuclear Ru2(CO)4 sawhorse structure, the diruthenium backbone being bridged by the carboxylato ligands, while the two phosphine ligands occupy the axial positions at the ruthenium atoms. However, chiral carbon atoms in the carboxylic acid undergo racemisation during the thermal reaction. 相似文献
15.
Roberto Della Pergola Luigi Garlaschelli Carlo Manassero Donatella Strumolo Emanuela Grigiotti 《Inorganica chimica acta》2009,362(2):331-338
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
16.
Thiolato-bridged tri- and dinuclear platinum complexes of the types [Pt3(μ-SR)4(dppm)2]2+ (1) and [Pt2(μ-ER)2(dppm)2]2+ (2) (E=S or Se; R=alkyl or aryl; dppm=bis(diphenylphosphino)methane) have been prepared using the mononuclear precursors [Pt(ER)2(dppm)]. The complexes have been characterized by NMR (1H, 13C, 31P, 195Pt), FT-IR and FAB mass spectral data. The structure of [Pt3(μ-SC6H4CH3-4)4(dppm)2][CF3SO3]2 · 6CH2Cl2 (1d), has been established through X-ray crystallography, revealing a zig-zag arrangement of the three coordination spheres around the platinum atoms. 相似文献
17.
An oxalate-bridged binuclear iron(III) complex, [(acac)2Fe(μ-ox)Fe(acac)2], (acac−=acetylacetonate anion and ox2−=oxalate anion) was prepared. The complex crystallized as two types of crystals under different conditions: one had 1,2-dichloroethane as a solvent molecule of crystallization 2, the other did not 1. Both compounds have been characterized by X-ray crystallography, infrared spectroscopy, and thermogravimetric analysis. Compound 1 has also been characterized by UV-Vis and 1H NMR spectroscopies, mass spectrometry, and electrochemistry. In both crystals, each iron(III) is coordinated in an octahedral arrangement by the oxygen atoms of an oxalate-bridging ligand and four oxygen atoms belonging to peripheral acac ligands in an octahedral arrangement. The intermetallic distance of Fe?Fe is 5.4368(9) Å in 1 and 5.438(2) Å in 2. Two iron(III) ions in each crystal are bridged by the oxalate and both lie in the oxalate-plane. The results of thermal analyses imply that the thermal stability of 2 is lower than that of 1. Cyclic voltammograms of 1 in acetonitrile and dichloromethane at low temperature showed two consecutive, quasi-Nernstian, one-electron reduction steps corresponding to the reduction of FeIII-FeIII to FeIII-FeII followed by the reduction of FeIII-FeII to FeII-FeII. The electrochemical comproportionation constants (Kc) of the equilibrium (FeIII-FeIII) + (FeII-FeII) ? 2(FeIII-FeII) are 108.9 in acetonitrile medium and 108.5 in dichloromethane, respectively. The considerably large Kc values indicate that the main factor contributing to the stabilization of the FeIII-FeII mixed-valence state is electronic delocalization through the oxalate-bridge. 相似文献
18.
The cationic carbyne complex [Cp(CO)2MnCC6H5]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
19.
Oguejiofo T. Ujam William Henderson Brian K. Nicholson 《Inorganica chimica acta》2010,363(13):3558-126
Alkylation reactions of the nucleophilic platinum(II) sulfide complex [Pt2(μ-S)2(PPh3)4] with functionalised alkylating agents have been investigated as a versatile synthetic route to dinuclear, cationic sulfide-thiolate complexes of the type [Pt2(μ-S)(μ-SR)(PPh3)4]+, extending the range of thiolate complexes that can be prepared using this methodology. A wide range of functional groups can be incorporated, using appropriate alkylating agents, and include ketone, ester, amide, hydrazone, semicarbazone, thiosemicarbazone, oxime, guanidine, urea and thiourea groups. 相似文献
20.
Some novel hydrido-anions of general formula [Ir4H(CO)9(μ-L-L)]− (L-L = Ph2PCH(CH3)PPh2, Ph2P(CH2)2PPh2, Ph2P(CH2)3PPh2 and Ph2AsCH2AsPh2) have been obtained by the reaction of [Ir4(CO)10(μ-L-L)] with the base 1,8-diazabicyclo[5.4.0]undec-7-ene in wet dichloromethane. According to IR and 1H, 31P and 13C NMR data at low temperature, these anionic derivatives display a single conformation in solution: three edge-bridging COs around the triangular basal face and both the hydride and the bidentate ligands located in axial positions relative to this face. The structures of four compounds were established by X-ray diffraction studies, which confirmed the configuration proposed on the basis of spectroscopic data. 相似文献