共查询到20条相似文献,搜索用时 31 毫秒
1.
Clovis Peppe Fabiano Molinos de Andrade Jaqueline Pinto Vargas Melina de Azevedo Mello Railander Alves Barcellos Robert A. Burrow Rubia Mara Siqueira da Silva 《Journal of organometallic chemistry》2009,694(14):2228-2233
Halogenomethyl-dihalogen-indium(III) compounds X2InCH2X (X = Br, I) obtained from indium monohalides and methylene dihalides were reacted with the soft donor ligands dialkylsulfides, R2S (R = CH3, CH2Ph) to afford the corresponding dialkylsulfonium methylide complexes of InX3, X3InCH2SR2 (X = Br, R = CH3, 1; X = I, R = CH3, 2; X= I, R = CH2Ph, 3). Compound 1 was reacted with the hard donor ligands dimethylsulfoxide or triphenylphosphine oxide to give the corresponding 1:1 adduct, Br3(L)InCH2S(CH3)2 (L = (CH3)2SO, 4; L = (C6H5)3PO, 5). Compounds 1-5 were fully characterized in solution by NMR spectroscopy and in the solid state by X-ray methods. 相似文献
2.
Sailer Santos dos Santos Gelson Manzoni de Oliveira 《Journal of organometallic chemistry》2007,692(14):3081-3088
TeX4 (X = Cl, Br) react in HCl/HBr with [Ph(CH3)2Te]X (X = Cl, Br) to give [PhTe(CH3)2]2[TeCl6] (1) and [PhTe(CH3)2]2[TeBr6] (2). The reaction of PhTeX3 (X = Cl, Br, I) in cooled methanol with [(Ph)3Te]X (X = Cl, Br, I) leads to [Ph3Te][PhTeCl4] (3), [Ph3Te][PhTeBr4] (4) and [Ph3Te][PhTeI4] (5). In the lattices of the telluronium tellurolate salts 1 and 2, octahedral TeCl6 and TeBr6 dianions are linked by telluronium cations through Te?Cl and Te?Br secondary bonds, attaining bidimensional (1) and three-dimensional (2) assemblies. The complexes 3, 4 and 5 show two kinds of Te?halogen secondary interactions: the anion-anion interactions, which form centrosymmetric dimers, and two identical sets of three telluronium-tellurolate interactions, which accomplish the centrosymmetric fundamental moiety of the supramolecular arrays of the three compounds, with the tellurium atoms attaining distorted octahedral geometries. Also phenyl C-H?halogen secondary interactions are structure forming forces in the crystalline structures of compounds 3, 4 and 5. 相似文献
3.
Gelson Manzoni de Oliveira Gleison Antônio Casagrande Rozanna Marques Muzzi 《Journal of organometallic chemistry》2009,694(15):2463-2444
(PhSe)2 reacts with Br2, ethylenethiourea and PhTeBr3, further with I2, ethylenethiourea and PhTeI3, to give [PhSe(etu)][PhTeBr4] (1) (Ph = phenyl; etu = ethylenethiourea) and [PhSe(etu)][PhTeI4] (2) in very good yields.The tellurium centers present a distorted octahedral configuration, achieved through dimerization involving secondary, reciprocal Te···X interactions.In both compounds the anionic dimmers are linked through X···X interactions, attaining a one-dimensional, polymeric assembly along the b axis. Cations and anions are linked through short Se···X contacts. In addition to single crystal X-ray data, multinuclear NMR results for 1 and 2 are also presented and discussed. 相似文献
4.
Ya Chen Jian-Shi Jin Zhi-Gang Zou Xiao-Zeng You 《Journal of organometallic chemistry》2009,694(5):763-43
Rhenium(I) tricarbonyl complexes with bispyridine ligands bearing sulfur-rich pendant, Re(CO)3(Medpydt)X (Medpydt = dimethyl 2-(di(2-pyridyl)methylene)-1,3-dithiole-4,5-dicarboxylate; X = Cl, 1; X = Br, 2) and Re(CO)3(MebpyTTF)X (MebpyTTF = 4,5-bis(methyloxycabonyl)-4′,5′-(4′-methyl-2,2′-dipyrid-4-ylethylenedithio)-tetrathiafulvalene; X = Cl, 5; X = Br, 6), were prepared from the reactions between Re(CO)5X (X = Cl, Br) and Medpydt or MebpyTTF, respectively. Hydrolysis of the above complexes afforded the analogues with carboxylate derivatives, Re(CO)3(H2dpydt)X (X = Cl, 3; X = Br, 4) and Re(CO)3(H2bpyTTF)X (X = Cl, 7; X = Br, 8). The crystal structures for complexes 1 · 2H2O, 5 and 6 were determined using X-ray single crystal diffraction. UV-Vis absorption spectra of the rhenium complexes show the intraligand and MLCT transitions. Electrochemical behaviors of all new compounds were studied with cyclic voltammetry. Upon irradiation, complexes 3-6 exhibit blue to red emissions in fluid solutions at the room temperature. The performance of complexes 3, 4, 7 and 8 as photosensitizers for anatase TiO2 solar cells was preliminarily investigated as well. 相似文献
5.
Ph2SiCl2 and PhMeSiCl2 react with Li2E (E = S, Se, Te) under formation of trimeric diorganosilicon chalcogenides (PhRSiE)3 (R = Ph: 1a-3a, R = Me: cis/trans-4a (E = S), cis/trans-5a (E = Se)). In case of E = S, Se dimeric four-membered ring compounds (PhRSiE)2 (R = Ph: 1b-2b, R = Me: cis/trans-4b (E = S), cis/trans-5b (E = Se)) have been observed as by-products. 1a-5b have been characterized by multinuclear NMR spectroscopy (1H, 13C, 29Si, 77Se, 125Te). Four- and six-membered ring compounds differ significantly in 29Si and 77Se chemical shifts as well as in the value of 1JSiSe.The molecular structures of 2a, 3a and trans-5a reported in this paper are the first examples of compounds with unfused six-membered rings Si3E3 (E = Se, Te). The Si3E3 rings adopt twisted boat conformations. The crystal structure of 3a reveals an intermolecular Te-Te contact of 3.858 Å which yields a dimerization in the solid state. 相似文献
6.
Alexey Zazybin 《Journal of organometallic chemistry》2007,692(24):5375-5382
[(RR′-admpzp)2Ti(OPri)2] complexes (2a-c), synthesized from reaction of Ti(OPri)3Cl (0.5 equiv) with 1-dialkylamino-3-(3,5-dimethyl-pyrazol-1-yl)-propan-2-ol compounds in the presence of triethylamine (0.5 equiv), are pseudo-octahedral with each RR′-admpzp ligand κ2-O,N(pyrazolyl) coordinated to the titanium center. In solution, 2a-c adopt isomeric structures that are in dynamic equilibrium. At 23 °C, 2a-c/1000 MAO catalyst systems furnished high molecular weight polymers with narrow molecular weight distributions (Mw/Mn = 2.7-2.8). At 100 °C, 2a-c/MAO catalyst systems exhibited increased polymerization activity and 2c/1000 MAO system furnished high molecular weight polyethylene with a molecular weight distribution (Mw/Mn = 2.1) that is close to that found for single-site catalysts. 相似文献
7.
Reactions of bis(pyridin-2-yl)ketone with tin tetrahalides, SnX4 (X = Cl or Br), or organotin trichlorides, R′SnCl3 (R′ = Ph, Bu or CH2CH2CO2Me), in ROH (R = Me or Et) readily produces RObis(pyridin-2-yl)methanolato)tin complexes, [5: RO(py)2C(OSnX3)] (5: R,X = Me,Cl; Et,Cl; Et,Br) or [6: MeO(py)2C(OSnCl2R′)] (R′ = Ph, Bu, CH2CH2CO2Me). In addition, halide exchange reaction between SnI4 and (5: R,X = Me,Cl) occurred to give (5: R,X = Me,I). The crystal structures of six tin(IV) derivatives indicated, in all cases, a monoanionic tridentate ligand, [RO(py)2C(O−)-N,O,N], arranged in a fac manner about a distorted octahedral tin atom. The Sn–O and Sn–N bonds lengths do not show much variation amongst the six complexes despite the differences in the other ligands at tin. 相似文献
8.
Alexander A. Korlyukov Mikhail Yu. Antipin Aleksander I. Albanov Eleonora A. Zel’bst 《Journal of organometallic chemistry》2009,694(5):607-615
The reaction of fluorosilanes XYSiF2 (X = Y = F; X = F, Y = Ph; X = Ph, Y = Me) with diethanolamines and their O-trimethylsilyl derivatives affords novel Si-fluoro substituted quasisilatranes 3, 5 and 9. These compounds were characterized by the multinuclear NMR spectroscopy and X-ray diffraction analysis. Experimental and theoretically calculated electron density distribution functions in crystal structure of 9 have shown that the N → Si coordination bond corresponds to polar bond with pronounced ionic contribution. Calculated N → Si bond order in the compound 9 does not exceed 1/3 of the normal Si-N bond. A strong N → Si coordination bond exists in compounds 3, 5 and 9 the length of which varies in the range 1.98-2.175 Å. 相似文献
9.
Ara Núñez-MontenegroRosa Carballo José M. Hermida-RamónEzequiel M. Vázquez-López 《Polyhedron》2011,30(12):2146-2156
N-thioamide thiosemicarbazone derived from 4-(methylthio)benzaldehyde (R = H, HL1; R = Me, HL2 and R = Ph, HL3) have been prepared and their reaction with fac-[ReX(CO)3(CH3CN)2] (X = Br, Cl) in methanol gave the adducts [ReX(CO)3(HLn)] (1a X = Cl, n = 1; 1a′ X = Br, n = 1; 1b X = Cl, n = 2; 1b′ X = Br, n = 2; 1c X = Cl, n = 3; 1c′ X = Br, n = 3) in good yield.All the compounds have been characterized by elemental analysis, mass spectrometry (ESI), IR and 1H NMR spectroscopic methods. Moreover, the structures of HL2, HL3, HL3·(CH3)2SO and 1b′·H2O were also elucidated by X-ray diffraction. In 1b′, the rhenium atom is coordinated by the sulphur and the azomethine nitrogen atoms (κS,N3) forming a five-membered chelate ring, as well as three carbonyl and bromide ligands. The resulting coordination polyhedron can be described as a distorted octahedron.The structure of the dimers is based on rhenium(I) thiosemicarbazonates [Re2(L1)2(CO)6] (2a), [Re2(L2)2(CO)6] (2b) and [Re2(L3)2(CO)6] (2c) as determined by X-ray studies. Methods of synthesis were optimized to obtain amounts of these thiosemicarbazonate complexes. In these compounds the dimer structures are achieved by Re-S-Re bridges, where S is the thiolate sulphur from a κS,N3-bidentate thiosemicarbazonate ligand.Some single crystals isolated in the synthesis of 2b contain [Re(L4)(L2)(CO)3] (3b) where L4 (=2-methylamine-5-(para-methylsulfanephenyl)-1,3,4-thiadiazole) is originated in a cyclization process of the thiosemicarbazone. Furthermore, the rhenium atom is coordinate by the sulphur and the thioamidic nitrogen of the thiosemicarbazonate (κS,N2) affording a four-membered chelate ring. 相似文献
10.
Bhaskar Biswas Pallepogu Raghavaiah Núria Aliaga-Alcalde Jhy-Der Chen Rajarshi Ghosh 《Polyhedron》2010
The neutral hexadentate Schiff base N-(1-pyridin-2-yl-phenylidene)-N′-[2-({2-[(1-pyridin-2-yl-phenylidene)amino]ethyl}amino)ethyl]ethane-1,2-diamine (L) was used to synthesize new lanthanide(III) complexes of type [M(L)(NCS)3] (M = La, 1; Gd, 2; Tb, 3; Dy, 4). Single crystal X-ray diffractometry reveals the tricapped trigonal prismatic structure of all the compounds. Variable-temperature magnetic susceptibility measurements in 2–4 show the expected χMT versus T plot for an isolated, mononuclear lanthanide(III) ion with 4f7, 4f8 and 4f9 configurations, respectively following Curie Law. 相似文献
11.
Michael I. Bruce Marcus L. Cole Brian W. Skelton 《Journal of organometallic chemistry》2006,691(22):4601-4614
Complexes M(CCCSiMe3)(CO)2Tp′ (Tp′ = Tp [HB(pz)3], M = Mo 2, W 4; Tp′ = Tp∗ [HB(dmpz)3], M = Mo 3) are obtained from M(CCCSiMe3)(O2CCF3)(CO)2(tmeda) (1) and K[Tp′].Reactions of 2 or 4 with AuCl(PPh3)/K2CO3 in MeOH afforded M{CCCAu(PPh3)}(CO)2Tp′ (M = Mo 5, W 6) containing C3 chains linking the Group 6 metal and gold centres.In turn, the gold complexes react with Co3(μ3-CBr)(μ-dppm)(CO)7 to give the C4-bridged {Tp(OC)2M}CCCC{Co3(μ-dppm)(CO)7} (M = Mo 7, W 8), while Mo(CBr)(CO)2Tp∗ and Co3{μ3-C(CC)2Au(PPh3)}(μ-dppm)(CO)7 give {Tp∗(OC)2Mo}C(CC)2C{Co3(μ-dppm)(CO)7} (9) via a phosphine-gold(I) halide elimination reaction. The C3 complexes Tp′(OC)2MCCCRu(dppe)Cp∗ (Tp′ = Tp, M = Mo 10, W 11; Tp′ = Tp∗, M = Mo 12) were obtained from 2-4 and RuCl(dppe)Cp∗ via KF-induced metalla-desilylation reactions. Reactions between Mo(CBr)(CO)2Tp∗ and Ru{(CC)nAu(PPh3)}(dppe)Cp∗ (n = 2, 3) afforded {Tp∗(OC)2Mo}C(CC)n{Ru(dppe)Cp∗} (n = 2 13, 3 14), containing C5 and C7 chains, respectively. Single-crystal X-ray structure determinations of 1, 2, 7, 8, 9 and 12 are reported. 相似文献
12.
H.W. Peindy N’Dongo 《Journal of organometallic chemistry》2009,694(6):981-1500
We describe reactions of [99mTc(H2O)3(CO)3)]+ (1) with Diels-Alder products of cyclopentadiene such as “Thiele’s acid” (HCp-COOH)2 (2) and derivatives thereof in which the corresponding [(Cp-COOH)99mTc(CO)3)] (3) complex did form in water. We propose a metal mediated Diels-Alder reaction mechanism. To show that this reaction was not limited to carboxylate groups, we synthesized conjugates of 2 (HCp-CONHR)2 (4a-c) (4a, R = benzyl amine; 4b, R = Nα-Boc-l-2,3-diaminopropionic acid and 4c, R = glycine). The corresponding 99mTc complexes [(4a)99mTc(CO)3)] 6a, [(4b)99mTc(CO)3)] 6b and [(4c)99mTc(CO)3)] 6c have been prepared along the same route as for Thiele’s acid in aqueous media demonstrating the general applicability of this synthetic strategy. The authenticity of the 99mTc complexes on the no carrier added level have been confirmed by chromatographic comparison with the structurally characterized manganese or rhenium complexes.Studies of the reaction of 1 with Thiele’s acid bound to a solid phase resin demonstrated the formation of [(Cp-COOH)99mTc(CO)3)] 3 in a heterogeneous reaction. This is the first evidence for the formation of no carrier added 99mTc radiopharmaceuticals containing cyclopentadienyl ligands via solid phase syntheses. Macroscopically, the manganese analogue 5a and the rhenium complexes 5b-c have been prepared and characterized by IR, NMR, ESI-MS and X-ray crystallography for 5a (monoclinic, P21/c, a = 9.8696(2) Å, b = 25.8533(4) Å, c = 11.8414(2) Å, β = 98.7322(17)°) in order to unambiguously assign the authenticity of the corresponding 99mTc complexes. 相似文献
13.
14.
Syntheses of complexes of the type [ML(NO3)2], where M = Co(II), Ni(II), and Cu(II), L = N-(2-pyridylethyl)pyridine-2-carbaldimine, a tridentate ligand, are described. They were characterized by elemental analysis, spectral, magnetic, thermal studies, and X-ray crystallography. In the cobalt (1), nickel (2), and copper (3) complexes, the bivalent metal ion is coordinated by the three nitrogen atoms of the tridentate L with two pyridine-N groups occupying trans positions. Amongst the two nitrates one coordinates in a bidentate fashion while the other adopts a monodentate fashion. The X-band EPR spectra of 1, 2, and 3 in the polycrystalline state and in acetonitrile solution at 77 K are reported. Room temperature vibrating sample magnetometer data of 1, 2, and 3 afforded μeff values respectively of 3.928, 3.897, and 1.952 BM. The thermal stability order is 1 > 2 > 3, showing a reverse Irving-Williams trend. 相似文献
15.
Schiff base N,N′-bis(salicylidene)-p-phenylenediamine (LH2) complexed with Pt(en)Cl2 and Pd(en)Cl2 provided [Pt(en)L]2 · 4PF6 (1) and Pd(Salen) (2) (Salen = N,N′-bis(salicylidene)-ethylenediamine), respectively, which were characterized by their elemental analysis, spectroscopic data and X-ray data. A solid complex obtained by the reaction of hexafluorobenzene (hfb) with the representative complex 1 has been isolated and characterized as 3 (1 · hfb) using UV–Vis, NMR (1H, 13C and 19F) data. A solid complex of hfb with a reported Zn-cyclophane 4 has also been prepared and characterized 5 (4 · hfb) for comparison with complex 3. The association of hfb with 1 and 4 has also been monitored using UV–Vis and luminescence data. 相似文献
16.
The salts [S(NMe2)3][MF6] (M = Nb, 2a; M = Ta, 2b) and [S(NMe2)3][M2F11] (M = Nb, 2c; M = Ta, 2d) have been prepared by reacting MF5 (M = Nb, 1a; M = Ta, 1b) with [S(NMe2)3][SiMe3F2] (TASF reagent) in the appropriate molar ratio. The solid state structure of 2b has been ascertained by X-ray diffraction. The 1:1 molar ratio reactions of 1a with a variety of organic compounds (L) give the neutral adducts NbF5L [L = Me2CO, 3a; L = MeCHO, 3b; L = Ph2CO, 3c; L = tetrahydrofuran (thf), 3d; L = MeOH, 3e; L = EtOH, 3f; L = HOCH2CH2OMe, 3g; L = Ph3PO, 3h; L = NCMe, 3i] in good yields. The complexes MF5L [M = Nb, L = HCONMe2, 3j; M = Nb, L = (NMe2)2CO, 3k; M = Ta, L = (NMe2)2CO, 3l; M = Nb, L = OC(Me)CHCMe2, 3m] have been detected in solution in admixture with other unidentified products, upon 2:1 molar reaction of 1 with the appropriate reagent L. The ionic complexes [NbF4(tht)2][NbF6], 4a, and [NbF4(tht)2][Nb2F11], 4b, have been obtained by combination of tetrahydrothiophene (tht) and 1a, in 1:1 and 2:3 molar ratios, respectively. The treatment of 1 with a two-fold excess of L leads to the species [MF4L4][MF6] [M = Nb, L = HCONMe2, 5a; M = Ta, L = HCONMe2, 5b; M = Nb, L = thf, 5c; M = Ta, L = thf, 5d; M = Nb, L = OEt2, 5e]. The new complexes have been fully characterised by NMR spectroscopy. Moreover, the revised 19F NMR features of the known compounds MF5L [M = Ta, L = Me2CO, 3n; M = Ta, L = Ph2CO, 3o; M = Ta, L = MePhCO, 3p; M = Ta, L = thf, 3q; M = Nb, L = CH3CO2H, 3r; M = Nb, L = CH2ClCO2H, 3s; M = Ta, L = CH2ClCO2H, 3t], TaF4(acac), TaF4(Me-acac) and [TaF(Me-acac)3][TaF6] (Me-acac = methylacetylacetonato anion) are reported. 相似文献
17.
Zhanfeng Li Haisheng Xu Huaiming Hu Jiwu Wang 《Journal of organometallic chemistry》2009,694(14):2210-438
Two new charge-transfer salts, [CpFeCpCH2N(CH3)3]4[PMo12O40] · CH3CN (1) and [CpFeCpCH2N(CH3)3]4[GeMo12O40] (2), were synthesized by the traditional solution synthetic method and their structures were determined by single-crystal X-ray analysis. Salt 1 belongs to the triclinic space group P1, and salt 2 belongs to the triclinic space group . There exist the complex interactions of the cationic ferrocenyl donor and Keggin polyanion in the solid state. The solid state UV-Vis diffuse reflectance spectra indicate the presence of a charge-transfer band climbing from 450 nm to well beyond 900 nm for 1, a charge-transfer band from 460 to 850 nm with λmax = 630 nm for 2.The EPR spectra of salts 1 and 2 at 77 K show a signal at g = 2.0048 and 1.9501, respectively, ascribed to the delocalization of one electron in reduced Keggin ion in salt 1 and the MoVI in [GeMo12O40]4− is partly reduced to MoV owing to the charge-transfer transitions taking place between the ferrocenyl donors and the POM acceptors. The two compounds were also characterized by IR spectroscopy and cyclic voltammetry. 相似文献
18.
H.J. Breunig T. Borrmann O. Moldovan R.P. Wagner 《Journal of organometallic chemistry》2009,694(3):427-91
Syntheses of [Me3SbM(CO)5] [M = Cr (1), W (2)], [Me3BiM(CO)5] [M = Cr (3), W (4)], cis-[(Me3Sb)2Mo(CO)4] (5), [tBu3BiFe(CO)4] (6), crystal structures of 1-6 and DFT studies of 1-4 are reported. 相似文献
19.
Xiu-Li Wang Yan-Feng Bi Hong-Yan Lin Guo-Cheng Liu Bao-Kuan Chen 《Journal of organometallic chemistry》2007,692(20):4353-4360
Three novel metal-organic frameworks [M(1,3-BDC)(Dpdq)(H2O)m] · nH2O, (M = CoII (1), CdII (2) or ZnII (3); m = 0, 1; n = 0, 1, 2, respectively) have been obtained from hydrothermal reactions of three different metal(II) nitrates with the same mixed ligands [isophthalic acid (1,3-BDC) and 2,3-di-2-pyridylquinoxaline (Dpdq)], and structurally characterized by elemental analyses, IR spectroscopy, and single-crystal X-ray diffraction analyses. Single-crystal X-ray analyses show that each pair of metal ions are bridged by various coordination modes of 1,3-BDC ligands to form left- and right-handed helical chains in 1, linear chains in 2, and double chains in 3, respectively. N-containing flexible ligand Dpdq takes a chelating coordination mode acting as terminal ligand. In the compound 1, adjacent left- and right-handed helical chains are packed through hydrogen bonds to form a two-dimensional (2-D) structure. In the compounds 2 and 3, adjacent chains are further linked by hydrogen bonds and/or π-π stacking interactions to form a three-dimensional (3-D) distorted hexagon meshes supramolecular framework for 2 and a ZnS-related three-dimensional (3-D) topology for 3, respectively. The different structures of compounds 1-3 illustrate that the influence of the metal ions in the self-assembly of polymeric coordination architectures. In addition, compounds 2 and 3 exhibit blue emission in the solid state at room temperature. 相似文献
20.
Ni(II) complexes (1–5) of di-2-pyridyl ketone N(4)-phenylthiosemicarbazone (HL) have been synthesized and spectrochemically characterized. Elemental analyses revealed a NiL2 · 2H2O stoichiometry for compound 1. However, the single crystals isolated revealed a composition NiL2 · 0.5(H2O)0.5(DMF). The compound crystallizes into a monoclinic lattice with the space group P21/n. Complexes 2, 3 and 4 are observed to show a 1:1:1 ratio of metal:thiosemicarbazone:gegenion, with the general formula NiLX · yH2O [X = NCS, y = 2 for 2; X = Cl, y = 3 for 3 and X = N3, y = 4.5 for 4]. Compound 5 is a dimer with a metal:thiosemicarbazone:gegenion ratio of 2:2:1, with the formula [Ni2L2(SO4)] · 4H2O. 相似文献