共查询到20条相似文献,搜索用时 15 毫秒
1.
Kathryn M. Carlson-Day Thomas E. Concolino Judith L. Eglin Chun Lin Tong Ren Edward J. Valente Jeffrey D. Zubkowski 《Polyhedron》1996,15(24):4469
The singlet-triplet separations for the edge-sharing bioctahedral (ESBO) complex W2(μ-H)(μ-Cl)(Cl4(μ-dppm)2 · (THF)3 (II) has been studied by 31P NMR spectroscopy. The structural characterization of [W2(μ-H)2(μ-O2CC6H5)2Cl2(P(C6H5)3)2] (I) by single-crystal X-ray crystallography has allowed the comparison of the energy of the HOMOLUMO separation determined using the Fenske-Hall method for a series of ESBO complexes with two hydride bridging atoms, two chloride bridging atoms and the mixed case with a chloride and hydride bridging atom. The complex representing the mixed case, [W2(μ-H)(μ-Cl)Cl4(μ-dppm)2 · (THF)3] (II), has been synthesized and the value of −2J determined from variable-temperature 31P NMR spectroscopy. 相似文献
2.
Pavel A. Abramov Maxim N. Sokolov Alexander V. Virovets Eugenia V. Peresypkina Vladimir P. Fedin 《Journal of Cluster Science》2007,18(3):597-605
Reaction of [MoOCl5]2− with in situ generated H2Se under hydrothermal conditions (4M HCl, 140 °C) leads to reduction of Mo(V) to Mo(IV) with the formation of a triangular
cluster Mo3(μ3-Se)(μ-O)34+ in high yield. It is present in HCl solutions as aqua chlorocomplex [Mo3(μ3-Se)(μ-O)3(H2O)6Cl3]+ which was isolated and structurally characterized as supramolecular adduct with cucurbit[6]uril (CB[6]), {[Mo3(μ3-Se)(μ-O)3(H2O)6Cl3]2CB[6]}Cl2·15H2O.
Dedicated to Professor Dieter Fenske on the Occasion of his 65th Birthday 相似文献
3.
The emission spectra of a series of molybdenum(II) chloride clusters containing thiolate ligands, [Mo6(μ3-Cl)8(SR)6]2− (R = Et, Bu, Ph, Bn), have been recorded. These complexes all show a broad emission at ~700 nm after excitation at 337, 400
and 410 nm. Determination of the excited state lifetimes and quantum yields of these complexes in acetonitrile reveals that
(Bu4N)2[Mo6(μ3-Cl)8(SPh)6] displays the longest excited state lifetime of this series (26 μs at 296 K).
相似文献
Lisa F. SzczepuraEmail: |
4.
A novel trinuclear supramolecular compound of [Cd3Cl6C6N2O8H22]
n
has been synthesized under alanine with cadmium chloride to the reaction in aqueous solution conditions, and characterized
by elemental analyses, FT-IR spectroscopy, X-ray diffraction, DTA-TG. Its crystal structure was determined from single crystal
X-ray diffraction. The title compound crystallizes in monoclinic system with space group P21/n. The crystal structure of the compound is characterized by forming a trinuclear 3D supramolecular structure with three cadmium(II)
ions, six chloride ions, two molecules D, L-alanine in salt, two coordinated water molecules and two crystal water molecules.
Cd(1) is distorted octahedrally coordinated with two oxygen atoms (from the adjacent amino acid and water molecule) and four
chloride ions; Cd(2) is smaller extent distorted octahedrally coordinated with two oxygen atoms (from the adjacent amino acids)
and four chloride ions. Cd(1) and Cd(2) connected by the bridge bonds of μ2-Cl, μ3-Cl and the carboxyl oxygen into ID chain structure, which further connected by hydrogen bonds to form 3D supramolecular network.
Fluorescence test showed that the compound has a good photoluminescence property, respectively. 相似文献
5.
Pavel A. Abramov Maxim N. Sokolov Alexandr V. Virovets Eugenia V. Peresypkina Cristian Vicent Vladimir P. Fedin 《Journal of Cluster Science》2009,20(1):83-92
Reaction of [Mo6(μ3-Cl)8Cl6]2− with H2Se, generated in situ from ZnSe and 4 M HCl under hydrothermal conditions lead to the substitution of one or two bridging
chlorides, depending on the reagents ratio. With the Mo6/ZnSe 1:3 molar ratio [Mo6(μ3-SeCl7)Cl6]3− forms selectively in high yield. Further substitution is more hindered, and even at 1:20 cluster-to-selenide molar ratio
a mixture of [Mo6(μ3-SeCl7)Cl6]3− and [Mo6(μ3-Se2Cl6)Cl6]4− is formed. The products were characterized by X-ray, Raman spectra and electrospray ionization mass spectrometry. 相似文献
6.
A series of complexes containing Cu(N-N)2Cl2 (N-N=bis(pyrazol-1-yl)methane (bpzm), bis(3,5dimethylpyrazol-1-yl)methane (bdmpzm), 2,2-dipyridylamine (dpa), 5,6-diphenyl-3-(2-pyridyl)-1,2,4-trazine (dppt) and 2,2′-bipyridine (bipy)), Cu(N-N-N)Cl2 (N-N-N=2,2′:6′,2″-terpyridine (terpy)) and HgCl2 building blocks have been synthesized and structurally characterized. Increase in structural dimensionality is observed for [Cu(bpzm)2][HgCl4], [Cu(dpa)2][HgCl3]2 and [Cu(terpy)(μ-Cl)HgCl3] compounds. No coordination polymers have formed in the case of bis(3,5dimethylpyrazol-1-yl)methane, 5,6-diphenyl-3-(2-pyridyl)-1,2,4-trazine and 2,2′-bipyridine. The [Cu(bpzm)2][HgCl4] and [Cu(terpy)(μ-Cl)HgCl3] complexes have been studied by magnetic measurements. 相似文献
7.
Jian-Liang Zhou Qi-Yuan Chen Ying-Ying Gu Guang-Quan Mei Hua-Wu Yang 《Transition Metal Chemistry》2005,30(8):1036-1041
Coordination polymers {[Et4N][Ag2I3]}n (1) and [CuBr(C10H8N2S2)]n (2) were prepared by standard Schlenk techniques. Their X-ray measurements indicate that polymer (1) crystallizes in the orthorhombic space group Pnma, and polymer (2) crystallizes in the monoclinic space group P21/n. Complex (1) has a hanging ladder-like polymeric chain which can also be described as a helical chain bridged by Ag–Ag edges. Complex
(2) exhibits a monoclinic crystal system with a slightly distorted tetrahedron. The nonlinear optical (NLO) properties of (1) and (2) were investigated by using Z-scan techniques with an 8 ns pulsed laser at 532 nm. These two coordination polymers exhibit
NLO absorption and an effective self-focusing effect. The effective α2 and n2 values of cluster (1) are 3.04×10−11 m W−1 and 7.6×10−18 m2 w−1 and the effective α2 and n2 values of compound (2) are 1.08×10−11 m W−1 and 3.1×10−18 m2 w−1 when measured in CH2Cl2 solution. 相似文献
8.
Reaction of 2-(phenylazo)pyridine (pap) with [Ru(PPh3)3X2] (X = Cl, Br) in dichloromethane solution affords [Ru(PPh3)2(pap)X2]. These diamagnetic complexes exhibit a weakdd transition and two intense MLCT transitions in the visible region. In dichloromethane solution they display a one-electron
reduction of pap near − 0.90 V vs SCE and a reversible ruthenium(II)-ruthenium(III) oxidation near 0.70 V vs SCE. The [RuIII(PPh3)2(pap)Cl2]+ complex cation, generated by coulometric oxidation of [Ru(PPh3)2(pap)Cl2], shows two intense LMCT transitions in the visible region. It oxidizes N,N-dimethylaniline and [RuII(bpy)2Cl2] (bpy = 2,2′-bipyridine) to produce N,N,N′,N′-tetramethylbenzidine and [RuIII(bpy)2Cl2]+ respectively. Reaction of [Ru(PPh3)2(pap)X2] with Ag+ in ethanol produces [Ru(PPh3)2(pap)(EtOH)2]2+ which upon further reaction with L (L = pap, bpy, acetylacetonate ion(acac−) and oxalate ion (ox2−)) gives complexes of type [Ru(PPh3)2(pap)(L)]n+ (n = 0, 1, 2). All these diamagnetic complexes show a weakdd transition and several intense MLCT transitions in the visible region. The ruthenium(II)-ruthenium(III) oxidation potential
decreases in the order (of L): pap > bpy > acac− > ox2−. Reductions of the coordinated pap and bpy are also observed. 相似文献
9.
(NEt4)2[WIVO(S2C2(CN)2)2] (1), isolated by reaction of Na2 WO4, Na2S2C2(CN)2 (Na2mnt) in acidified (pH5.5) aqueous medium in the presence of excess of sodium dithionite and NEt4Br, reduces CO2/HCO
3
−
(pH 7.5) to yield HCOO− and (NEt4)2[WVIO2(S2C2(CN)2)2] (2) mimicking tungsten-formate dehydrogenase (W-FDH) activity. (1) reacts with Na2MoO4 in acidic medium to produce [MoIvO(S2C2(CN)2)2]2− implicating the displacement of tungsten by molybdenum from the cofactor complex in W-FDH. 相似文献
10.
Tahra Ayed Nathalie Guihéry Bahoueddine Tangour Jean-Claude Barthelat 《Theoretical chemistry accounts》2006,116(4-5):497-504
Correlated ab initio calculations have been performed on three dipalladium(I) complexes. These compounds differ both by the metal–metal interaction and by the metal–ligand interaction. The [Pd2Cl2(μ −H2PCH2PH2)2] complex exhibits a σ overlap between the two binding metallic orbitals and has no bridging ligand. In [Pd2Cl4(μ −CO)2]2−, the leading interaction between the two palladium involves a π overlap between the metallic orbitals and goes through the two bridging CO ligands. In [Pd2Cl2(μ −CO)(μ −H2PCH2 PH2)2], a single CO ligand bridges the two palladium atoms which interact through a hybrid σ–δ overlap. The three compounds also differ by the metal–metal distances. Surprisingly enough, while the palladium atoms are formally d
9 in all these complexes, none of them is paramagnetic. We propose here a detailed analysis of the electronic structures of these compounds and rationalize their chemical structures as well as the role of back-donation in the CO bridged compounds. Finally, since highly correlated treatments are used to describe these complexes, a detailed study of the role of both non-dynamical and dynamical correlations is performed. Concerning the [Pd2Cl4(μ −CO)2]2− complex, this analysis has revealed that the complex is not bound at the lowest correlated levels of calculation and therefore dynamical correlation is alone responsible for its binding energy. 相似文献
11.
Trinuclear mixed-valence Co(III)-Co(II)-Co(III) complex {CoIII(μ-Sal2MePn)(N3)(μ1,1-N3)}2CoII(H2O)2 (I) was synthesized by the reaction of Co(NO3)2 · 6H2O with the Schiff base ligand H2Sal2MePn condensed from 2,2-dimethylpropylenediamine with salicylaldehyde and characterized by elemental analyses and FT-IR spectroscopy.
The molecular structure of I has been determined from single-crystal X-ray diffraction analysis. In this structure, the N3− anions show both terminal and μ1,1-bridging modes. The terminal Co(III) centers exhibit uniform arrangements of the Schiff-base ligand and N3− anions. 相似文献
12.
The reaction of HgCl2 and Te(R)CH2SiMe3 [R = CH2SiMe3 (1), Ph (2)] in ethanol yielded a mononuclear complex [HgCl2{Te(R)CH2SiMe3}2] (R = Ph, 3a; R = CH2SiMe3, 3b). The recrystallization of 3a or 3b from CH2Cl2 produced a dinuclear complex [Hg2Cl2(μ-Cl)2{Te(R)CH2SiMe3}2] (R = Ph, 4a; R = CH2SiMe3, 4b). When 3a was dissolved in CH2Cl2, the solvent quickly removed, and the solid recrystallized from EtOH, a stable ionic [HgCl{Te(Ph)CH2SiMe3}3]Cl·2EtOH (5a·2EtOH) was obtained. Crystals of [HgCl2{Te(CH2SiMe)2}]·2HgCl2·CH2Cl2 (6b·2HgCl2·CH2Cl2) were obtained from the CH2Cl2 solution of 3b upon prolonged standing. The complex formation was monitored by 125Te-, and 199Hg NMR spectroscopy, and the crystal structures of the complexes were determined by single crystal X-ray crystallography. 相似文献
13.
S. B. Artemkina M. S. Tarasenko A. V. Virovets N. G. Naumov 《Russian Journal of Coordination Chemistry》2012,38(4):257-263
Heterometallic chloride complexes [Mo5NbI8Cl6]
n− (n = 2, 3) are synthesized. The crystal structures of their salts are determined: for (Ph4P)2[Mo5NbI8Cl6] (I), triclinic crystal system, spacegroup P
[`1]\bar 1, a = 10.9886(6), b = 11.4604(5), c = 13.4343(7) ?, α = 66.124(2), β = 86.892(2), γ = 86.490(2)°, Z = 1, V = 1543.35(13) ?3; and for (4-MePyH)5[Mo5NbI8Cl6]Cl2 (II), monoclinic crystal system, space group C2/m, a = 16.4937(4), b = 14.7335(3), c = 11.6534(3) ?, β = 99.8750(10)°, Z = 2, V = 2789.94(11) ? The geometric parameters of compounds I and II and the conditions for the formation of the complexes with the charges −2 and −3 are discussed. 相似文献
14.
The reactions (I) Hg2Cl2(s) + Br2(g) and (II) HgCl2(s) + HgBr2(s) have been investigated by an X-ray method. Both the reactions yield two forms of the mixed halide HgClBr, designated as α-HgClBr and β-HgClBr. The cell parameters of the two are as follows:α-HgClBr: , , , z = 4, ? = 5.91 g/cm3. The powder pattern and cell parameters are similar to that of HgCl2. Therefore it is probable that the chlorine atoms, in the linear halogenHghalogen molecules of HgCl2 structure have been replaced by bromines, and since the radius of the bromine atom is larger than that of chlorine, the lattice is larger in this case.β-HgClBr: , , , z = 4, ? = 5.40. These parameters are the same as those reported in the literature for β-Hg(ClBr)2, and its X-ray powder pattern is similar to HgCl2. Therefore this phase also has linear halogenHghalogen molecules but the distribution of Cl and Br atoms is perhaps random.Heating the products (I) and (II) up to the melting point increases the amount of α phase and decreases the β phase, whereas crystallization increases the β phase. DTA study has supported the X-ray findings. 相似文献
15.
Malcolm H. Chisholm Judith C. Gallucci Carl B. Hollandsworth 《Journal of Cluster Science》2005,16(2):231-249
Alcoholysis of W2(NMe2)6 with excess n-propanol in hexane yields the tetranuclear cluster, W4(OPrn, I. Reduction of I with two equivalents of Li2COT in THF gives a small yield of Li2W2(OPrn)8. Single crystals were isolated by cooling the product mixture in DME and were shown to be [Li2W2(OPrn)8(DME)]2, II, which consists of a unique “dimer of dimers” structure. In this reaction sequence, W416+ cluster formation is followed by four electron reduction to reform the (W≡W)6+ unit. Better yields of the lithium salt can be obtained by the addition of LiOPrn/HOPrn solutions to W2(OBut)6 in which case Li2W2(OPrn)8 has been obtained as a 1:1 adduct with LiOPr. This identity of this salt was confirmed by solution NMR spectroscopy. In the alternative reaction, the (W≡W)6+ center remains intact from reactant to product. No attempt has been made to separate the product from excess LiOPr. DFT (ADF 2004.01) molecular orbital calculations on the model cluster W4(OH)16 are used to help elucidate the disruption of the W4 cluster upon four electron reduction. The molecular structures of compounds I and II are reported.*Dedicated to Professor F. A Cotton on the occasion of his 75th birthday. 相似文献
16.
A. Leineweber 《Journal of solid state chemistry》2003,176(1):198-202
A re-interpretation and re-evaluation of single-crystal X-ray diffraction data of a previously reported ‘(NH4)2(NH3)[Ni(NH3)2Cl4]’ (J. Solid State Chem. 162 (2001) 254) give a new formula (NH4)2−2z[Ni(NH3)2]z[Ni(NH3)2Cl4] with z=0.152. This new formula results from defects in an idealized ‘(NH4)2[Ni(NH3)2Cl4]’ basic structure, where two adjacent NH4+ cations are replaced by one Ni(NH3)22+ unit. Cl− anions from the basic structure complete the coordination sphere of the new Ni2+ to [Ni(NH3)2Cl4]2−. 相似文献
17.
D. M. Kuzyaev G. K. Fukin E. V. Baranov M. N. Bochkarev 《Russian Chemical Bulletin》2007,56(10):1960-1963
The reaction of neodymium diiodide NdI2 with excess methanol in acetonitrile produced the tetranuclear neodymium cluster [Nd4(μ2-I)1.1(μ3-I)(μ2-OMe)4.9(μ4-O)(MeCN)12]I3 (1). In the latter, the isomorphic substitution of one methoxy group by an I− anion with site occupancies (%) of 90 and 10, respectively, was observed. Due to the isomorphic substitution in the crystal,
cluster 1 can be considered as a superposition of two complexes, [Nd4(μ2-I)(μ3-I)(μ2-OMe)5(μ4-O)(MeCN)12]I3 and [Nd4(μ2-I)2(μ3-I)(μ2-OMe)4(μ4-O)(MeCN)12]I3. The characteristic feature of cluster 1 is that the center of the Nd4 cage is occupied by the μ4-coordinated O2− anion, which is indicative of the partial O-C bond cleavage in methanol. The reaction of NdI2 with an equimolar amount of MeOH in an acetonitrile solution produced methoxide NdI2(OMe)(MeCN)4 in 49% yield.
Dedicated to Professor W. J. Evans on the occasion of his 60th birthday.
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 10, pp. 1894–1897, October, 2007. 相似文献
18.
S. V. Larionov V. L. Varand R. F. Klevtsova T. G. Leonova L. A. Glinskaya E. M. Uskov 《Russian Journal of Coordination Chemistry》2008,34(12):931-937
The heteroligand complex Nd(Phen){(iso-C4H9)2PS2}2(NO3) (I) was synthesized and its IR spectrum was analyzed. The anions (iso-C4H9)2PS2/− and N3/− act as bidentate cyclic ligands. The single crystals of [Nd(Phen){iso-C4H9)2PS2}3] (II) were obtained on evaporation of a solution of complex I in a mixture CH2Cl2-hexane and were studied by X-ray diffraction. Crystals II are triclinic: a = 10.5509(5); b = 14.7432(8), c = 16.8503(10) ?; α = 102.882(2)°, β = 97.211(2)°, γ= 108.087(2)°, V = 2374(2) ?3, Z = 2, ρ(calcd.) = 1.332 g/cm3, space group . The coordination polyhedron of the Nd atom in a separate mononuclear molecule II is a distorted dodecahedron N2S6. The molecules are bound by weak van der Waals and π-π interactions. The photoluminescence spectra of complexes I, II were measured and interpreted.
Original Russian Text ? S.V. Larionov, V.L. Varand, R.F. Klevtsova, T.G. Leonova, L.A. Glinskaya, E.M. Uskov, 2008, published
in Koordinatsionnaya Khimiya, 2008, Vol. 34, No. 12, pp. 944–950. 相似文献
19.
Reactions between tungsten halides are discussed along the series of compounds WCl6 → WCl4 → W6Cl12 ↔ W6Cl18 → [W6CCl18]n− ← [W3Cl13]u−, focusing on the two closely related tungsten chloride compounds whose structures compromise the well-known octahedro W6Cl18 cluster and the carbon-centered triprismo W6CCl18 cluster. Both clusters can be regarded as being built by merging two trigonal [W3Cl13]u− units in different ways. Syntheses, structural transformation reactions, and concepts regarding electronic structures are
reported. 相似文献
20.
Felipe Gómez-de la Torre Yolanda Gutiérrez Félix A. Jalón Blanca R. Manzano Ana Rodríguez 《Monatshefte für Chemie / Chemical Monthly》2000,35(5):1267-1280
Partial removal of chloride anions from the dimer [Pd(η3-2-CH3*C3H4)(μ-Cl)]2 with AgTf(Tf = CF3SO3) followed by addition of dppm affords [Pd2(η3-Me*C3H4)2(μ-Cl)(μ-dppm)]Tf (1). The substitution of Cl− by X− (X = pz, SC6F5, S py ) using the appropriate salts yields the new derivatives [Pd2(η3-Me*C3H4)2(μ-X)(μ-dppm)]Tf (2–4). All complexes exhibit a dinuclear half-A-frame structure with two isomers present in solution. The isomers differ in the relative orientation of the two allyl groups (cis or trans). The isomer interconversion was studied by variable temperature 1H NMR spectroscopy. The molecular structures of 2 and 4 were solved by X-ray diffraction studies. A distorted boat conformation of the seven- or six-membered metallacycle was found in both cases. 相似文献