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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.
[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
4.
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
5.
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
6.
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
7.
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
8.
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
9.
10.
The reaction of cyanamide and its derivatives with the (η5-C5H5)Mn(CO)2(THF) and (η5-C5H4CH3)Mn(CO)2(THF) complexes affords the cyanamide substituted complexes of types (η5-C5H5)Mn(CO)2(NCN(R′)(R″)) (2a-d) and (η5-C5H4CH3)Mn(CO)2(NCN(R′)(R″)) (3a-e). All complexes were characterized by spectroscopy (1H, 13C NMR, IR), elemental and mass spectroscopy analysis. Complex 2b (η5-C5H5)Mn(CO)2(NCN(CH3)2) was additionally examined by single crystal X-ray structure determination. 相似文献
11.
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
12.
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
13.
Kazuhiro Kawabata 《Inorganica chimica acta》2005,358(6):2082-2088
[Ir(η5-C5Me5)(C8H4S8)] (1) [ = 2-{(4,5-ethylenedithio)-1,3-dithiole-2-ylidene}-1,3-dithiole-4,5-dithionate(2−)] was reacted with iodine in dichloromethane to afford one-electron- and two-electron-oxidized species [IrI(η5-C5Me5)(C8H4S8)] (2), [IrI(η5-C5Me5)(C8H4S8)](I3) (3) and [IrI(η5-C5Me5)(C8H4S8)](I5) (4). The oxidized species exhibit electrical conductivities of (1.1-5.0) × 10−6 S cm−1 measured for compacted pellets at room temperature. The X-ray crystal structures of the two-electron-oxidized complexes 3 and 4 revealed the Ir-I bonds for both of them and the presence of for 3 and ions for 4 as the counter anions. They have many S-S and S-I non-bonding contacts to form two-dimensional molecular interaction sheets in the solid state. 相似文献
14.
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
15.
Cátia Ornelas José Mesquita M. Helena Garcia Nelson Lopes Kalle Nättinen 《Inorganica chimica acta》2005,358(8):2482-2488
The bimetallic cyano-bridged [(η5-C5H5)(PPh3)2Ru(μ-CN)Ru(PPh3)2(η5-C5H5)][PF6] (1) was prepared by reaction of [(η5-C5H5)(PPh3)2RuCl] with N,N′-bis(cyanomethyl)ethylenediamine. The single crystal structure determined by X-ray diffraction showed crystallization on the triclinic P1 space group with a perfect alignment of the cyanide bridges. This accentric crystallization was explored having in view the NLO properties at the macroscopic level, determined by the Kurtz Powder technique. Besides the very low efficiency values for the second harmonic generation, the value obtained for the bimetallic complex 1 showed to be higher than one of the parent complex [(η5-C5H5)(PPh3)2RuCN] (2). 相似文献
16.
Matthew A. Cranswick Olivia Oorhles-Steele Nicolai Burzlaff Dennis L. Lichtenberger 《Inorganica chimica acta》2008,361(4):1122-1133
The metal-sulfur bonding present in the transition metal-thiolate complexes CpFe(CO)2SCH3, CpFe(CO)2StBu, CpRe(NO)(PiPr3)SCH3, and CpRe(NO)(PPh3)SCH3 (Cp = η5-C5H5) is investigated via gas-phase valence photoelectron spectroscopy. For all four complexes a strong dπ-pπ interaction exists between a filled predominantly metal d orbital of the [CpML2]+ fragment and the purely sulfur 3pπ lone pair of the thiolate. This interaction results in the highest occupied molecular orbital having substantial M-S π∗ antibonding character. In the case of CpFe(CO)2SCH3, the first (lowest energy) ionization is from the Fe-S π∗ orbital, the next two ionizations are from predominantly metal d orbitals, and the fourth ionization is from the Fe-S π orbital. The pure sulfur pπ lone pair of the thiolate fragment is less stable than the filled metal d orbitals of the [CpFe(CO)2]+ fragment, resulting in a Fe-S π∗ combination that is higher in sulfur character than the Fe-S π combination. Interestingly, substitution of a tert-butyl group for the methyl group on the thiolate causes little shift in the first ionization, in contrast to the shift observed for related thiols. This is a consequence of the delocalization and electronic buffering provided by the Fe-S dπ-pπ interaction. For CpRe(NO)(PiPr3)SCH3 and CpRe(NO)(PPh3)SCH3, the strong acceptor ability of the nitrosyl ligand rotates the metal orbitals for optimum backbonding to the nitrosyl, and the thiolate rotates along with these orbitals to a different preferred orientation from that of the Fe complexes. The initial ionization is again the M-S π∗ combination with mostly sulfur character, but now has considerable mixing among several of the valence orbitals. Because of the high sulfur character in the HOMO, ligand substitution on the metal also has a small effect on the ionization energy in comparison to the shifts observed for similar substitutions in other molecules. These experiments show that, contrary to the traditional interpretation of oxidation of metal complexes, removal of an electron from these metal-thiolate complexes is not well represented by an increase in the formal oxidation state of the metal, nor by simple oxidation of the sulfur, but instead is a variable mix of metal and sulfur content in the highest occupied orbital. 相似文献
17.
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
18.
Reactions of [Re2(CO)10] with Me3NO and diphosphines [Ph2P(CH2)nPPh2, n=1-6] yield mixtures of the monodentate-coordinated diphosphine complexes [Re2(CO)9(η1-P-P)] (P-P=Ph2P(CH2)nPPh2, n=1-6) (yields 5-40%) and bridged dimers [{Re2(CO)9}2(μ-P-P)] (5-50%). These complexes were isolated as either equatorial or axial isomers, or a mixture of two isomers. Reactions of the monodentate complexes with Me3NO yield close-bridged complexes [Re2(CO)8(μ-P-P)] and phosphine oxide complexes [Re2(CO)9{P-P(O)}]. The structures of the close-bridged complexes 1 (n=3) and 2 (n=4), were determined by X-ray crystallography. The Re-Re bond in the close-bridged complex with the longest phosphine chain (n=6) is readily cleaved in CDCl3 to give the complex [{cis-ReCl(CO)4}2(μ-dpph)] (3) as the product, the structure of which was also determined by X-ray crystallography. 相似文献
19.
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
20.
Masahiko Maekawa Yojiro Kayanuma Takayoshi Kuroda-Sowa Megumu Munakata 《Inorganica chimica acta》2005,358(4):1313-1316
The single crystals of dichloro-bridged dinuclear Rh-Cp* complex with neutral Me2CO molecules, [Rh2(Cp*)2(μ-Cl)2(Me2CO)2](BF4)2 (Cp* = η5-C5Me5), was isolated and the structure was in first determined crystallographically. 相似文献