共查询到20条相似文献,搜索用时 31 毫秒
1.
A. L. Gushchin K. A. Kovalenko M. N. Sokolov D. Yu. Naumov E. V. Peresypkina A. V. Virovets V. P. Fedin 《Russian Chemical Bulletin》2007,56(9):1707-1711
The reactions of the oxalate complexes [M3Q7(C2O4)3]2− (M = Mo or W; Q = S or Se) with MnII, CoII, NiII, and CuII aqua and ethylenediamine complexes in aqueous and aqueous ethanolic solutions were studied. The previously unknown heterometallic
complexes [Mo3Se7(C2O4)3Ni(H2O)5]·3.5H2O (1) and K3{[Cu(en)2H2O]([Mo3S7(ox)3]2Br)}·5.5H2O (2) were synthesized. In these complexes, the oxalate clusters serve as monodentate ligands. The K(H2en)2[W3S7(C2O4)3]2Br·4H2O salt (3) was isolated from solutions containing CoII, NiII, or CuII aqua complexes and ethylenediamine. The reaction of [Mo3Se7(C2O4)3]2− with HBr produced the bromide complex [Mo3Se7Br6]2−, which was isolated as (Bu4N)2[Mo3Se7Br6] (4). Complexes 1–3 were characterized by X-ray diffraction, IR spectra, and elemental analysis. The formation of 4 was detected by electrospray mass spectrometry.
Dedicated to Academician G. A. Abakumov on the occasion of his 70th birthday.
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 1645–1649, September, 2007. 相似文献
2.
Kentaro Takano Hideki Kawasaki Genta Sakane Takashi Shibahara 《Journal of Cluster Science》2007,18(3):684-696
The reaction of a sulfur and oxygen-bridged 8-quinolinolato trinuclear molybdenum cluster [Mo3OS3(qn)3(H2O)3]+ (3; Hqn = 8-quinolinol) with equimolar amounts of acetylene carboxylic acid, 4-pentynoic acid, 5-hexynoic acid, acetic acid,
and pimelic acid gave clusters having μ-carboxylato groups, [Mo3OS3(qn)3(H2O)(μ-HC≡CCOO)] (6), [Mo3OS3(qn)3(H2O)(μ-HC≡C(CH2)2COO)] (7), [Mo3OS3(qn)3(H2O)(μ-HC≡C(CH2)3COO)] (8), [Mo3OS3(qn)3(H2O)(μ-CH3COO)] (4), and [{Mo3OS3(qn)3(C2H5OH)}2(μ-C7H10O4)] (5), respectively. X-ray structural analyses, 1H NMR, and electronic spectra of these clusters made clear that each of the COO− groups of the reagents bridges two Mo atoms in each cluster and that no adduct formation occurred at the sulfurs in the clusters.
The reaction of 3 with a large excess-molar amount (50 times) of acetylene carboxylic acid gave [Mo3OS(μ3-SCH=C(COOH)S)(qn)3(H2O)(μ-HC≡CCOO)] (9) with two molecules of acetylene carboxylic acid, one acting as a carboxylato bridge and the other in adduct formation, as
supported by the electronic and 1H NMR spectra. The corresponding aqua cluster [Mo3OS3(H2O)9]4+ (1), on the contrary, reacts with acetylene carboxylic acid to give adduct [Mo3OS(μ3-SCH=C(COOH)S)(H2O)9]4+ (2).
Electronic supplementary material The online version of this article (doi:) contains supplementary material, which is available to authorized users. 相似文献
3.
A. L. Gushchin M. N. Sokolov K. A. Kovalenko E. V. Peresypkina A. V. Virovets N. I. Alferova V. P. Fedin 《Russian Journal of Coordination Chemistry》2009,35(6):395-400
The reactions between [Mo3(μ3-S)(μ2-S)3(Acac)3(Py)3]PF6 (HAcac is acetylacetone, Py is pyridine) and CuX (X = Cl, I, SCN) afford heterometallic cubane clusters [Mo3(CuX)(μ3-S)4(Acac)3(Py)3]PF6. The structures of two new compounds, [Mo3(CuCl)S4(Acac)3(Py)3]PF6 · 3.25CH2Cl2 · 0.5C6H5CH3 and [Mo3(CuI)S4(Acac)3(Py)3]PF6 · 4C6H6, are determined by X-ray diffraction analysis. All synthesized compounds are characterized by elemental analysis and IR spectra. According to the vibrational spectra, the thiocyanate complex in the solid state is a mixture of the bond isomers [Mo3(CuNCS)S4(Acac)3(Py)3]PF6 and [Mo3(CuSCN)S4(Acac)3(Py)3]PF6, whereas in solution this complex exists as a isothiocyanate form. 相似文献
4.
A new molybdophosphate (NH4)8{Mo2VO4[(Mo2VIO6)CH3C(O)(PO3)2]2}·14H2O (1), has been synthesized by the reaction of {Mo2VO4(H2O)6}2+ fragments with 1-hydroxyethylidenediphosphonate (hedp HOC(CH3)(PO3H2)2), and it is characterized by 31P NMR, IR, UV, element analysis, TG and single-crystal X-ray analysis. The structure analysis reveals that the polyoxoanion
can be described as two {(Mo2VIO6)(CH3C(O)(PO3)2} units connected by a {Mo2VO4}2+ moiety. In the structure, the six Mo atoms are arranged into a new “W-shaped” structure, which represents a new kind of molybdophosphate. 相似文献
5.
The new alkoxysilyl-functionalized alkynes [HC≡CCH2N(H)C(=O)N(H)(CH2)3Si(OEt)3] and [HC≡C(C6H4)–N(H)C(=O)N(H)(CH2)3Si(OEt)3] have been synthesized using literature methods. These have been reacted with Fe3(CO)12, Ru3(CO)12 and Co2(CO)8. With the iron carbonyl only decomposition was observed: with Ru3(CO)12 splitting of the alkynes into their parent components and formation of the complexes (μ-H)Ru3(CO)9[HC=N(CH2)3Si(OEt)3], (μ-H)Ru3(CO)9[C–C(C6H4)NH2] and (μ-H)2Ru3(CO)9[HC–CCH3] occurred. Finally, with Co2(CO)8 formation of complexes Co2(CO)6(HC2R) R=(C6H4)NH2, CH2NH(CO)NH(CH2)3Si(OEt)3, (C6H4)NH(CO)NH(CH2)3Si(OEt)3 containing the intact alkynes could be obtained. 相似文献
6.
Nikolay A. Pushkarevsky Sergey N. Konchenko Manfred Scheer 《Journal of Cluster Science》2007,18(3):606-617
The reaction of K2[Fe3(μ3-Q)(CO)9] (Q = Se (K2[1a]), Te (K2[1b])) with [(dppm)PtCl2] leads to the addition of a [(dppm)Pt]2+ unit to a Fe2Q face of the initial cluster. By this way new heteronuclear clusters [Fe3Pt(μ3-Q)(CO)9(dppm)] were obtained possessing a butterfly-shaped cluster core bridged by a μ4-Q unit. It has been found that the resulting Fe-Pt clusters exist as equilibrium mixtures of two isomeric forms in solution
differing by the dppm coordination mode: as a chelate ligand coordinated to Pt or as a bridging ligand coordinated to Pt and
Fe atoms. The mixtures of isomers can be separated by chromatography and the pure isomers can be isolated as stable crystalline
phases. Solutions of both isomers attain equilibrium at normal conditions in about 1 month as found by NMR.
Dedicated to Professor Dieter Fenske in the occasion of his 65th birthday. 相似文献
7.
A. L. Gushchin M. N. Sokolov D. Yu. Naumov V. P. Fedin 《Journal of Structural Chemistry》2008,49(4):748-752
By the reaction of [Mo3S4(C2O4)3(H2O)3]2− with PdCl2 and NH4H2PO2 as a reducing agent, followed by the addition of PPh3, a new oxalate cuboidal cluster complex [Mo3(PdPPh3)S4(C2O4)3(H2O)3]2− is obtained. It was isolated and structurally characterized as K2[Mo3(PdPPh3)S4(C2O4)3(H2O)3]·0.5H2O.
Original Russian Text Copyright ? 2008 by A. L. Gushchin, M. N. Sokolov, D. Yu. Naumov, and V. P. Fedin
__________
Translated from Zhurnal Strukturnoi Khimii, Vol. 49, No. 4, pp. 775–778, May–June, 2008. 相似文献
8.
The reactions of [RuCl2(PPh3)3] with 8-hydroxy-2-methyl-quinoline-7-carboxylic acid was examined, and a novel ruthenium(II) complex—[Ru(PPh3)2(C5H8NO)2]—was obtained. The compound was studied by IR, UV–vis spectroscopy, and X-ray crystallography. The molecular orbital diagram
of the complex was calculated with the density functional theory (DFT) method. The spin-allowed singlet–singlet electronic
transitions of the compound were calculated using the time-dependent DFT method, and the UV–vis spectrum of the compound was
discussed, on this basis. The luminescence property of the [Ru(PPh3)2(C5H8NO)2]was examined. 相似文献
9.
I. G. Fomina Zh. V. Dobrokhotova G. G. Aleksandrov O. Yu. Proshenkina M. L. Kovba A. S. Bogomyakov V. N. Ikorskii V. M. Novotortsev I. L. Eremenko 《Russian Chemical Bulletin》2009,58(1):11-20
Methods were developed for the controlled thermal synthesis of high-spin cubane-like pivalates {MII
4(μ3−OR)4} (M = Co or Ni; R = H or Me) starting from mono-and polynuclear complexes. The solid-state thermal decomposition of the known
pivalate clusters [MII
4(μ3−OMe)4−(μ2−OOCBut)2(η2−OOCBut)2(MeOH)4] and the new clusters [M4II(μ3)−OH4(η1−OOCBut)3−(μ−(NH2)2C6H2Me2)3(η1−(NH2)2C6H2Me2)3]+(OOCBut)− (M = Co or Ni) was studied by differential scanning calorimetry and thermogravimetry. The thermolysis of cubane-like CoII
and NiII pivalates is a destructive process. The phase composition of the decomposition products is determined by the nature
of coordinated ligands and the structural features of the metal core. 相似文献
10.
Two new heteropolyoxovanadoborates (H2dap)2H6{(VO)12O6[B3O6(OH)]6(H2O)}·13H2O (1, dap = 1,2-diaminopropane) and {[Zn(dien)]2[Zn(dien)(H2O)]4(VO)12O6[B3O6(OH)]6(H2O)}2·15H2O (2, dien = diethylenetriamine) have been hydrothermally synthesized and structurally characterized. Both 1 and 2 contain {(VO)12O6[B3O6(OH)]6(H2O)} cluster (denoted on V12B18), which is constructed by a puckered B18O36(OH)6 ring sandwiched between two triangles of six alternating cis and trans edge-sharing vanadium atoms, and a central water molecule. 1 consists of discrete [V12B18]10− cluster anions with H2dap2+ as counterions, while 2 consists of discrete neutral {[Zn(dien)]2[Zn(dien)(H2O)]4[V12B18]} clusters, which are built from two types of zinc(II) complex fragments connecting with V12B18 cluster through two Zn-(μ
3-O)-B bonds. Interestingly, 2 is the only example of the V12B18 cluster decorated by two types of zinc(II) complex fragments. 相似文献
11.
13C 2D-PASS spectra of two new cis-dioxo catecholatomolybdenum complexes (NH2CH2NH2CHCH2)2(H+)3[MovO
2(C6H4O2)2] and (NH2CH2CH2CH2NH2)2(H+)3[Mo(v)O2 (C2H2O2)2] have been obtained by solid-state nuclear magnetic resonance (NMR), in which the spinning sidebands were well-separated.
The principal components of the 13C shielding tensors were extracted by theoretically fitting the intensities of 13C spinning sidebands. The effects of counter cations on 13C chemical shift isotropy and shielding tensor of cis-dioxo catecholatomolybdenum complex anion [Mo (v)O2(C6H4O2)2]3− were studied, comparing the 13C CSA of those carbon sites in complex anions with that of the counter cations. Based on the known structure of the molybdenum
complex crystal, theoretical values of 13C shielding tensors were calculated by the ainitio GIAO method, in comparison with the experimental results. 相似文献
12.
S. P. Khranenko P. E. Plusnin L. A. Sheludyakova Yu. V. Gerasimova I. V. Korol’kov S. V. Korenev 《Russian Journal of Coordination Chemistry》2009,35(9):681-686
Complexation between crystalline trans-[Pd(H2O)2(NO3)2] and acetylacetone was studied. The complexes Pd2(Acac)2(μ-NO3)2(I) and Pd2(Acac)2(μ-Acac)(μ-NO3)(II) were obtained and examined by elemental analysis, X-ray powder diffraction analysis, differential scanning calorimetry,
simultaneous thermal analysis, mass spectrometry, and vibrational spectroscopy. 相似文献
13.
Jian-Long Xia Wei-Cheng Xiong Gang Chen Guang-Ao Yu Shan Jin Sheng-Hua Liu 《Transition Metal Chemistry》2009,34(4):389-393
Abstract Formal [2 + 2 + 2] addition reaction of [Cp*Ru(H2O)(NBD)][BF4] (NBD = norbornadiene) with 4,4′-Diethynylbiphenyl generates [C9H9-η6-C6H4(RuCp*)–C6H4(RuCp*)-η6-C9H9][BF4]2. The reaction of [Cp*Ru(H2O)(NBD)][BF4] with 1,4-diphenylbutadiyne generates the unusual [2 + 2 + 2] additional organic compound Ph–C≡C–C9H8–Ph in addition to the organometallic compound [Cp*Ru(η6-C6H5–C≡C–C≡C–Ph)][BF4]. [C9H9-η6-C6H4(RuCp*)–C6H4(RuCp*)-η6-C9H9][BPh4]2 is generated after the reaction of compound [C9H9-η6-C6H4(RuCp*)–C6H4(RuCp*)-η6-C9H9][BF4]2 with Na[BPh4]. The structure of this compound was confirmed by X-ray diffraction. A possible approach to form Ph–C≡C–C9H8–Ph and [Cp*Ru(η6-C6H5–C≡C–C≡C–Ph)][BF4] is suggested.
Graphical Abstract Formal [2 + 2 + 2] addition reaction of [Cp*Ru(H2O)(NBD)]BF4 (NBD = norbornadiene) with 4,4′-Diethynylbiphenyl generates [C9H9-η6-C6H4(RuCp*)–C6H4(RuCp*)-η6-C9H9][BF4]2. The reaction of [Cp*Ru(H2O)(NBD)][BF4] with 1,4-diphenylbutadiyne simply generates unusual [2 + 2 + 2] additional organic compound Ph–C≡C–C9H8–Ph in addition to the organometallic compound [Cp*Ru(η6-C6H5–C≡C–C≡C–Ph)][BF4]. [C9H9-η6-C6H4(RuCp*)–C6H4(RuCp*)-η6-C9H9][BPh4]2 is generated after the reaction of compound [C9H9-η6-C6H4(RuCp*)–C6H4(RuCp*)-η6-C9H9][BF4]2 with Na[BPh4]. The structure of this compound was confirmed by X-ray diffraction. And the possible approach to form Ph–C≡C–C9H8–Ph and [Cp*Ru(η6-C6H5–C≡C–C≡C–Ph)][BF4] was suggested.
Electronic supplementary material The online version of this article (doi:) contains supplementary material, which is available to authorized users. 相似文献
14.
A new reduced ferrous molybdophosphate composite solid of the formula, [(C10H14N2)H]4[FeII 10MoV 24(H2PO4)4(HPO4)12(PO4)4(H2O)16(OH)16O44]·12H2O, has been synthesized from a reaction mixture of MoO3, FeSO4·7H2O, C2H2O4·2H2O, nicotine, H3PO4, and H2O under hydrothermal conditions. The crystal data: monoclinic, space group C2/m, a = 24.4349(124), b = 12.9935(66), c = 14.7281(74) Å, β = 104.87(1) Å, V = 4520(4) Å3, Z = 2, R 1 = 0.0874, wR 2 = 0.2179. The structure is built from the building blocks of the formula, {FeII[Mo6P4O31]2}, consisting of a network of MO6 (M = Fe, Mo) octahedral and PO4 tetrahedral linked through their vertices. The connectivity of the building blocks with two pairs of face-sharing dinuclear Fe(II) clusters of the formula of [FeII 2(H2O)4O5] on which a phosphate group is hanging gives rise to one-dimensional chains with eight-membered apertures. The remarkable hydrogen bonded interactions between the chains form a unique and interesting framework with three-dimensional intersecting tunnels where the protonated nicotine molecules as structuring templates and crystallization water molecules are situated. 相似文献
15.
I. G. Fomina Zh. V. Dobrokhotova G. G. Aleksandrov M. L. Kovba V. I. Zhilov A. S. Bogomyakov V. M. Novotortsev I. L. Eremenko 《Russian Chemical Bulletin》2010,59(4):699-705
Joint thermolysis of the dinuclear pivalate complexes M2(μ-H2O)(μ-Piv)2(Piv)2(HPiv)4 (M = Co (1) and Ni (2), Piv- is the pivalate anion), in decane at 174 °C at the reactant ratio 1: 1 followed by treatment of the dry thermolysis product
with methanol afforded crystals of a new cocrystallization product of the molecules containing the heterometallic cubane-like
core M4(Co,Ni)O4. According to the X-ray diffraction data and the results of magnetic measurements, inductively coupled plasma atomic emission
spectrometry (ICP-AES), and investigations of the solid-state thermal decomposition products, the isolated cocrystallization
product has the general formula [Co1.6Ni2.4(μ3-OMe)4(μ2-Piv)2(pg2 -Piv)2(MeOH)4] ·4MeOH (3·4MeOH). Thermolysis of the crystals of the solvate 3·4MeOH is a destructive process accompanied by the intramolecular
redox reaction. A mixture of metallic Ni and cobalt oxide (CoO) are the final solid decomposition products of 3 · 4MeOH in
an argon atmosphere, whereas a mixture of the phases NiO, Co3O4, and NiCo2O4 is formed in air. 相似文献
16.
Narottam Gharah Basab Chattopadhyay Swarup K. Maiti Monika Mukherjee 《Transition Metal Chemistry》2010,35(5):531-539
(PPh4)2[MoO(O2)2(SHAH)]·H2O and PPh4[MoO(O2)2(HBA)] (SHAH3 = 2-hydroxybenzohydroxamic acid and HBAH = 2-hydroxybenzoic acid) have been synthesized and characterized by physico-chemical
and spectroscopic methods. In addition, the second complex has been structurally characterized by single-crystal X-ray diffraction
analysis. We have compared the catalytic activities of these two new complexes, together with the previously reported PPh4[MoO(O2)2(BZ)] (BZH = benzoic acid), with respect to the epoxidation of alkenes. The hydroxamate complex is the most efficient catalyst
among the three complexes, showing excellent catalytic activity for the substrates cyclohexene, cyclooctene, cinnamyl alcohol,
pent-4-en-1-ol and hex-1-ene. 相似文献
17.
Y. R. Zhao J. X. Dong Y. Liu S. S. Qu 《Journal of Thermal Analysis and Calorimetry》2007,90(2):565-568
The two complexes, [RE(Gly)4(Im)(H2O)](ClO4)3(s)(RE = Eu, Sm), have been synthesized and characterized. The standard molar enthalpies of reaction for the following reactions,
RECl3·6H2O(s)+4Gly(s)+Im(s)+3NaClO4(s) = =[RE(Gly)4(Im)(H2O)](ClO4)3(s)+3NaCl(s)+5H2O(l), were determined by solution-reaction colorimetry. The standard molar enthalpies of formation of the two complexes at
T = 298.15 K were derived as Δf
H
mΘ {Eu(Gly)4(Im)(H2O)}(ClO4)3(s)} = = −(3396.6±2.3) kJ mol−1 and Δf
H
mΘ {Sm(Gly)4(Im)(H2O)}(ClO4)3(s)} = −(3472.7±2.3) kJ mol−1, respectively. 相似文献
18.
The reaction of [RuCl2(PPh3)3] complex with dimethylpyrazole has been examined. A new ruthenium complex—[RuCl2(PPh3)2(3,5-Me2HPz)2] has been obtained and characterized by IR, 1H NMR and UV-VIS measurements. Crystal and molecular structure of the complex has been determined. The electronic structure
of the complex has been calculated by TDDFT method. 相似文献
19.
The heteropolytungstate (NH4)20[Na2(H2O)2Ni(H2O)5{Ni(H2O)}2As4W40O140] · 61H2O is obtained by the reaction of Na27[NaAs4W40O140] · 60H2O with NiCl2 · 6H2O and NH4Cl in pH≈4.0. The structure and chemical composition are determined by X-ray diffraction analysis and element analysis. The crystal data and main structure refinement are: a = 1.33135(18) nm, b = 1.9722(3) nm, c = 3.6430(5) nm, α = 78.010(2)°, β = 82.145(2)δ, γ = 74.385(2)°, V = 8.978(2) nm3, triclinic crystal system, space group: P1, Z = 2, R1 = 0.0512, and wR2 = 0.0684(I >2σ). The four S2 sites of the big cyclic ligand [As4W40O140]28- are occupied by two Na+ and two Ni2+ respectively, and each site supplies four Od coordinating to metal ion. The coordination number of Ni2+ is six, and that of two Na+ is five and six respectively. The third Ni2+ locates outside the cyclic [As4W40O140]28- and connects with one Od, and its coordination number is six. 相似文献
20.
Reaction of PPh2H with Pd(PPh3)4 in a 4:1 molar ratio produced the Pd complex with two diphenylphosphine ligands, Pd(PPh2H)2(PPh3)2 (1). Complex (1) was characterized by n.m.r. (1H and 31P{1H}) spectra as well as by elemental analysis. Reaction of (1) with RhCl(PPh3)3 yielded a Pd–Rh heterobimetallic complex with bridging phosphide ligands, formulated as [(Ph3P)2Pd(μ-PPh2)2Rh(PPh3)2]Cl (2). 相似文献