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1.
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   

2.
Reaction between [(C5H5)Co{P(O)(OEt)2}3]2UCl2 and neopentyl lithium affords the novel complex, [{η4-C5H5(CH2C(CH3)3)}Co{P(O)(OEt)2}3]2U, in which the uranium metal center has been dehalogenated and the neopentyl nucleophiles have attacked the cyclopentadienyl groups on the Kläui ([(C5H5)Co{P(O)(OEt)2}3]) ligands. The uranium atom in the title compound possesses octahedral geometry defined by the oxygen atoms from two sets of tripodal oxygen ligands, while the cyclopentadienyl ligands are bound η4 to the cobalt atoms. The formation of this complex suggests that the Kläui ligand may not be a suitable ligand framework for supporting organometallic complexes of oxophilic early actinides.  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.
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.
The U4+ cyclooctatetraenyl complex, [(C5Me5)(C8H8)U]2(μ-C8H8), 1, reacts with two equiv of 4,4′-dimethyl-2,2′-bipyridine (Me2bipy) and 2 equiv of 2,2′-bipyridine (bipy) to form 2 equiv of (η5-C5Me5)(η8-C8H8)U(Me2bipy-κ2N,N′) and (η5-C5Me5)(η8-C8H8)U(bipy-κ2N,N′), respectively. X-ray crystallography, infrared spectroscopy, and density functional theory calculations indicate that the products are best described as U4+ complexes of bipyridyl radical anions. Hence, only one of the (C8H8)2− ligands in 1 acts as a reductant and delivers 2 electrons per equiv of 1. Since the reduction potentials of uncomplexed (C8H8)2−, Me2bipy, and bipy are −1.86, −2.15, and −2.10 V vs SCE, respectively, it is likely that prior coordination of the bipyridine reagents enhances the electron transfer.  相似文献   

6.
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   

7.
The bimetallic cyano-bridged [(η5-C5H5)(PPh3)2Ru(μ-CN)Ru(PPh3)25-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   

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 reactivity of the metalloligand [Pt2(μ-S)2(PPh3)4] towards a variety of indium(III) substrates has been explored. Reaction with excess In(NO3)3 and halide (KBr or NaI) gave the four-coordinate adducts [Pt2(μ-S)2(PPh3)4InX2]+[InX4] (X = Br, I). An X-ray structure determination on the iodo complex revealed a slightly distorted tetrahedral coordination geometry at indium. In contrast, reaction of [Pt2(μ-S)2(PPh3)4] with indium(III) chloride was more complex; the ion [Pt2(μ-S)2(PPh3)4InCl2]+ was initially observed in solution (using ESI mass spectrometry), and isolated as its BPh4 salt. Analysis of [Pt2(μ-S)2(PPh3)4InCl2]+[BPh4] by ESI MS showed the parent cation when analysed in MeCN solution. However in solutions containing methanol, partial solvolysis occurred to give the di-indium species [{Pt2(μ-S)2(PPh3)4InCl(OMe)}2]2+ (proposed to contain an In2(μ-OMe)2 unit with five-coordinate indium) and its fragment ion [Pt2(μ-S)2(PPh3)4InCl(OMe)]+. Reaction of [Pt2(μ-S)2(PPh3)4] with InCl3·3H2O, 8-hydroxyquinoline (HQ) and trimethylamine in methanol gave the adduct [Pt2(μ-S)2(PPh3)4InQ2]+, isolated as its PF6 salt. The same cationic complex is formed when [Pt2(μ-S)2(PPh3)4] is reacted with InQ3 in methanol, but in this case the product is contaminated with the mononuclear complex [(Ph3P)2PtQ]+ formed by disintegration of the trinuclear complex [Pt2(μ-S)2(PPh3)4InQ2]+ with byproduct Q. [(Ph3P)2PtQ]+BPh4 was independently prepared from cis-[PtCl2(PPh3)2] and HQ/Me3N, and is the first example of a platinum 8-hydroxyquinolinate complex containing phosphine ligands.  相似文献   

10.
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   

11.
The reactivity of the bridged chloro borylene complex [μ-BCl{(η5-C5H4Me)Mn(CO)2}2] (2a) towards various protic reagents was studied. Reaction of 2a with isopropanol yielded the alkoxy borylene complex [μ-BOiPr{(η5-C5H4Me)Mn(CO)2}2] (3d) in very high yield. A further series of protic reagents HX (X=HS, BF4, Co(CO)4) gave, in the presence of pyridine, the new amino borylene complex [1-(μ-B)-4-H-(NC5H5){(C5H4Me)Mn(CO)2}2] (5a), which represents the product of an unprecedented 1,4-hydroboration of pyridine. Complex 5a was fully characterised in solution by multinuclear NMR studies, in the solid state by X-ray diffraction, and was also subject to DFT-studies.  相似文献   

12.
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 2b5-C5H5)Mn(CO)2(NCN(CH3)2) was additionally examined by single crystal X-ray structure determination.  相似文献   

13.
14.
The rhodium dimer [Rh2H(PPh2)2(PPh3)3] was prepared from RhCl(PPh3)3 and K4Sn9 in the presence of 2,2,2-cryptand in ethylenediamine/toluene solvent mixtures. The [K(2,2,2-crypt)]+ salt was isolated and characterized via NMR and X-ray diffraction studies. The solid state structure reveals a binuclear, diphenylphosphido-bridged, 32 electron Rh(I)-Rh(I) complex with edge-shared tetrahedral and square planar Rh centers with overall Cs point symmetry. 1-D and 2-D 1H, 31P, and 31P{1H} NMR experiments were used to characterize the complex.  相似文献   

15.
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   

16.
A method for the synthesis of titanocene (IV) aryl carboxylate complexes is presented in this paper. It is based on the fact that alcohol can catalyze the reaction between Cp2TiCl2 and aryl carboxylate ligands in the presence of sodium hydroxide (NaOH). The effects of the catalyst on the reaction system were studied and the possible reaction mechanism was proposed. This method was used to prepare a series of titanocene (IV) aryl carboxylate complexes and a macrocyclic titanocene (5,5′-dithiodisalicylato titanocene), whose structure was determined by X-ray diffraction analysis.  相似文献   

17.
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   

18.
Cu(C6H9N3O2)2Cl2对小麦的生态毒理效应   总被引:1,自引:0,他引:1  
陈怡平  刘永军 《生态学报》2005,25(11):3107-3111
以冬小麦为实验材料,比较研究了(1)不同浓度配合物对小麦生长的影响;(2)相同浓度的CuC l2、配体C6H9N3O2和配合物Cu(C6H9N3O2)2C l2对冬小麦种子萌发、苗期生长及其保护酶活性的影响。结果表明:与对照相比,(1)不同浓度新配合物对小麦生长具有不同程度的抑制作用,随着浓度的增高抑制作用逐渐增大;(2)CuC l2、配合物Cu(C6H9N3O2)2C l2对小麦种子总淀粉酶活性、蛋白酶活性、萌发率、生长势、根长、株高、总生物量均具有显著的抑制作用,配合物Cu(C6H9N3O2)2C l2的抑制作用小于CuC l2,而配体C6H9N3O2对上述生物学参数具有促进作用;(3)CuC l2、配合物Cu(C6H9N3O2)2C l2处理引起膜脂过氧化,显著的提高了幼苗的M DA浓度,导致SOD、POD、CAT活性降低,CuC l2的抑制作用大于配合物Cu(C6H9N3O2)2C l2,而配体C6H9N3O2处理对SOD、POD、CAT活性的提高有促进作用。上述结果说明C6H9N3O2对CuC l2生理胁迫具有保护作用,结合态的Cu2 (配合物Cu(C6H9N3O2)2C l2)的毒性显著的降低。在此基础上探讨了配合物抑制小麦生长发育的生物学机制。  相似文献   

19.
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   

20.
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   

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