共查询到20条相似文献,搜索用时 15 毫秒
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Ruth-Maria Olk A. Rhr J. Sieler K. Khler R. Kirmse W. Dietzsch E. Hoyer B. Olk 《无机化学与普通化学杂志》1989,577(1):206-216
Coordination Chemistry of 1,3-Dithiole-2-thione-4,5-diselenolate (dsit) — Comparison with 1,3-Dithiole-2-thione-4,5-dithiolate (dmit) Synthesis and properties of metal(II) and/or metal(III) bis-chelates of 1,3-dithiole-2-thione-4,5-diselenolate (dsit) of general type (Bu4N)n[M(dsit)2] (n = 2: M ? Zn, Cd, Hg, Cu, Ni, Pd, Pt; n = 1: M ? Ni, Au) are described. By comparison of the ir, 13C nmr, epr spectra, cyclovoltammetric data, and x-ray investigations (nickel-bis-chelates) of chelates of dsit and those of the chelates of 1,3-dithiole-2-thione-4,5-dithiolate (dmit) the consequences of selenium for sulfur substitution on position 4 and 5 of the heterocyclic ligand are discussed. 相似文献
3.
Ruth-Maria Olk Christiane Semmelmann R. Kirmse K. Khler E. Hoyer B. Olk 《无机化学与普通化学杂志》1990,581(1):59-68
Coordination Chemistry of 1,3-Thiaselenole-2-thione-4,5-dithiolate (dmits) – Comparison with 1,3-Dithiole-2-thione-4,5-dithiolate (dmit) Synthesis and properties of metal(II) and/or metal(III)-bis-chelates of 1,3-thiaselenole-2-thione-4,5-dithiolate (dmits) of the general type (Bu4N)n[M(dmits)2] (n = 2: M = Zn, Cd, Hg, Ni, Cu, Pd; n = 1: M = Au, Ni) are described. By comparison of the i.r., 13C-n.m.r., epr spectra and cyclovoltammetric data of chelates of dmits and those of 1,3-dithiole-2-thione-4,5-dithiolate (dmit) the consequences of the substitution of selenium for sulfur on position 3 of the heterocyclic ligand dmit are discussed. 相似文献
4.
合成了两种新的金属双噻吩类复合物:(苄基三乙基铵)双(1,3-二硫杂环戊烯-2-硫酮-4,5-二巯基)-金(BTEAADT)和(苄基三乙基铵)双(1,3-二硫杂环戊烯-2-硫酮-4,5-二巯基)-镍(BTEANDT).采用Z扫描方法,在皮秒脉冲下,分别测试了两种材料的乙腈溶液在532和1064nm的三阶非线性光学特性.Z扫描的结果表明,BTEAADT的乙腈溶液在532nm具有反饱和吸收效应,在1064nm非线性吸收效应可以忽略且在两种波长都有自散焦效应,三阶非线性折射率为负值.BTEANDT的乙腈溶液在532nm非线性吸收效应可以忽略,在1064nm具有饱和吸收效应且在两种波长都有自聚焦效应,三阶非线性折射率为正值.分析了造成这种差异的原因.经过计算得到了两种材料在532和1064nm的三阶非线性折射率,三阶非线性吸收系数,三阶非线性极化率和超极化率.BETAADT的非线性折射率在532nm为-1.685×10-18m2·W-1,在1064nm为-1.459×10-18m2·W-1;BTEANDT的非线性折射率在532nm为1.452×10-18m2·W-1,在1064nm为7.311×10-18m2·W-1.两种材料的三阶非线性吸收系数,三阶非线性极化率和超极化率的数量级分别是10-11m·W-1,10-13esu和10-31esu.结果表明这两种材料在非线性光学领域有潜在的应用价值. 相似文献
5.
《Journal of Coordination Chemistry》2012,65(23):3772-3781
The crystal structures and magnetic properties for two ion-pair complexes, [MG][Ni(dmit)2] (1) and [RhB][Ni(dmit)2] (2) (MG+ = N-(4-((4-(dimethylamino)phenyl)(phenyl)methylene)cyclohexa-2,5-dienylidene)-N-methylmethanaminium, RhB+ = 9-(2-carboxyphenyl)-3,6-bis(diethylamino)xanthylium; dmit2? = 1,3-dithiole-2-thione-4,5-dithiolate), have been investigated. Complex 1 crystallizes in the monoclinic space group P21/c, the stacking interactions between the GM+ and [Ni(dmit)2]? lead to the anion exhibiting a banana-shaped molecular geometry; the neighboring anions form a 1-D alternating chain along the crystallographic [1 1 0] direction via intermolecular lateral-to-lateral and head-to-head S ··· S contacts. The temperature dependence of magnetic susceptibility from 2–350 K does not display the magnetic character of a 1-D chain; the magnetic susceptibility data were fit to the Curie–Weiss equation to give C = 0.351(15) emu K mol?1, θ = ?3.51(28) K, and χ 0 = 8.00(3) × 10?5 emu mol?1. Complex 2 belongs to the triclinic space group P-1 with two crystallographic inequivalent [Ni(dmit)2]? anions, which exhibit perfect planar geometry. Two ethyl groups of RhB+ are disordered over two positions at 296 K, and one becomes ordered at 150 K. The [Ni(dmit)2]? anions form a 2-D molecular layer via intermolecular lateral-to-lateral and head-to-lateral S ··· S interactions with the anionic layer parallel to the crystallographic (0 1 ?1) plane. The temperature variation of magnetic susceptibility from 2 to 350 K shows that antiferromagnetic coupling dominates in the anionic layer, and the disorder–order changes of cationic structure are not coupled to magnetic property. 相似文献
6.
[see reaction]. A new and facile approach to 4-alkylthio-1,3-dithiole-2-thione starting from easily accessible reactants was described. This approach was based on the unusual reaction of a zinc complex of 1,3-dithiole-2-thione-4,5-dithiolate with electrophilic reagents in the presence of 3-picolyl chloride hydrochloride/or 4-picolyl chloride hydrochloride/or pyridine hydrochloride. 相似文献
7.
Syntheses and Properties of Molecular Conductors based on dmit isologous Chelates. Crystal and Molecular Structure of Tetramethylammonium-bis-[bis(1,3-dithiole-2-selone-4,5-diselenolato)nickelate]; [(CH3)4N] [Ni(dsise)2]2 Syntheses and properties of dichalcogenolate chelates of the general type [(CH3)4N]n[ML2] (n ≤ 2; M = Ni, Pd, Pt); L = dmit (1,3-dithiole-2-thione-4,5-dithiolate), dmise (1, 3-dithiole-2-selone-4,5-dithiolate), dsit (1, 3-dithiole-2-thione-4,5-diselenolate), dsise (1, 3-dithiole-2-selone-4,5-diselenolate), dsis (1, 3-diselenole-2-selone-4,5-diselenolate) are reported. The effects of the chalcogen atom variation in these chelates are discussed by using UV/VIS, IR, EPR, cyclovoltammetric and conductivity data. The x-ray structure of [(CH3)4N][Ni(dsise)2]2 (space group Pccn, a = 7.427(1), b = 39.144(5), c = 11.836(1) Å) and the conductivity of the crystal (12 S cm?1 at room temperature) are given. 相似文献
8.
S. Zeltner W. Dietzsch Ruth-Maria Olk R. Kirmse R. Richter U. Schrder B. Olk E. Hoyer 《无机化学与普通化学杂志》1994,620(10):1768-1776
Synthesis and Characterization of Metallocene Chelates of Heterocyclic 1,2-Dithiolates Synthesis and properties of metalocene dithiolene chelates Cp2ML with metal(IV) ions (M) of group IVA (Ti, Zr, Hf) and of vanadium with L = dmit (1,3-dithiole-2-thione-4,5-dithiolate), dmt (1,2-dithiole-3-thione-4,5-dithiolate), dmid (1,3-dithiole-2-one-4,5-dithiolate) and dmise (1,3-dithiole-2-selone-4,5-dithiolate) are described. The structures of these compounds were discussed using IR-, UV/VIS-, 1H-NMR-, 13C-NMR- and EPR data. The activation parameters of the chelate ring inversion of titanocene dithiolenes (Cp2TiL) and the x-ray structure of Cp2Ti(dmid) are given. 相似文献
9.
Samar Eid 《Journal of organometallic chemistry》2008,693(16):2755-2760
Cp2Ti(dithiolene) and Cp2Ti(diselenolene) complexes containing the N-methyl-1,3-thiazoline-2-thione-4,5-dithiolate ligand (Me-thiazdt), the N-phenyl-1,3-thiazoline-2-thione-4,5-dithiolate ligand (Ph-thiazdt) and the N-methyl-1,3-thiazoline-2-thione-4,5-diselenolate ligand (Me-thiazds) have been synthesized. Three approaches have been developed in order to generate the dithiolene or the diselenolene ligands which were reacted with Cp2TiCl2 to form the corresponding heteroleptic complexes. Their X-ray crystal structures, UV-Vis absorption spectra as well as their redox properties, determined by cyclic voltammetry have been investigated and discussed. Variable-temperature 1H NMR experiments have been performed in order to determine the activation energies of the chelate ring inversion. 相似文献
10.
Liu G Fang Q Xu W Chen H Wang C 《Spectrochimica acta. Part A, Molecular and biomolecular spectroscopy》2004,60(3):541-550
The higher frequency peak near 1050 cm(-1) of the doublet in the infrared and Raman spectra of 2-thione-1,3-dithiole-4,5-dithiolate (DMIT) derivatives corresponds mainly to the stretching vibration of carbon-sulfur double bond in the terminal S=CS2 fragments of DMIT skeletons while the lower one corresponds mainly to the Fermi resonance peak between overtones of symmetric stretching vibration of two carbon-sulfur single bond in the S=CS2 fragment of DMIT skeletons and the higher frequency. On the other hand, the higher frequency near 500 cm(-1) corresponds mainly to the symmetric stretching vibration of two carbon-sulfur single bond in the S=CS2 fragments of DMIT skeletons while the lower one corresponds mainly to the symmetric stretching vibration of the four carbon-sulfur single bond in the S2C=CS2 fragments of DMIT skeletons. 相似文献
11.
Lopes LJ Guerra AC Comerlato NM Turci CC Ferreira GB 《The journal of physical chemistry. A》2012,116(9):2244-2260
The S 1s X-ray absorption near edge structure (XANES) and X-ray photoelectron spectra (XPS) of the neutral complexes [SbL(dmit)] (L = Br or I; dmit =1,3-dithiole-2-thione-4,5-dithiolate) have been measured using tunable synchrotron radiation. The valence shell electronic excitation by ultraviolet-visible (UV-vis) spectroscopy and the infrared vibrational spectra are presented and analyzed. The UV-vis results lead to an assignment of bands at 400 nm as π(Sm) → π*(C═S), where S(m) is the thiolate sulfur. The corresponding S 1s → π*(C═S) transition was identified at 2468.3 eV. Ab initio calculations, within the improved virtual orbital (IVO) method, carried out with the GSCF3 program, were applied to establish a complete and accurate spectral assignment. It has been the first attempt to apply such methodology for dmit coordination compounds, and very consistent results were obtained. 相似文献
12.
Ruth-Maria Olk B. Olk J. Rohloff J. Reinhold J. Sieler Kirsten Trübenbach R. Kirmse E. Hoyer 《无机化学与普通化学杂志》1992,609(3):103-116
Coordination Chemistry of 1,3-Dithiole-2-selone-4,5-diselenolate (dsise) and 1,3-Dithiole-2-selone-4,5-dithiolate (dmise). Crystal and Molecular Structure of Tetrabutylammonium bis(1,3-dithiole-2-selone-4,5-diselenolato)nickelate(II) and -(III), [(n-C4H9)4N]2[Ni(dsise)2 and (n-C4H9)4[Ni(dsise)2] Syntheses and properties of metal(II) and metal(III) bis-chelates of 1,3-dithiole-2-selone-4,5-diselenolate (dsise), of the general type (Bu4N)n)M(dsise)2] (n =2 : M = Zn, Cd, Hg, Cu, Ni, Pd; n = 1: M = Ni, Au) are reported and compared with chelates of the isologue 1,3-dichalcogenole-2-chalcogenoe-4,5-dichalcogenolate (i. r., 13C-n. m. r., e. p. r., cyclovoltammetric data). The unexpected rearrangement during the syntheses of dsise and 1,3-dithiole-2-selone-4,5-diselenolate (dmise) is characterized by ab-initio SCF calculations. The x-ray structures of (Bu4N)2[Ni(dsise)2] (space group P21/c, a = 8.5556(13) Å, b = 15.0009(12) Å, c = 19.696(3) Å, β = 96.018(7)°, V = 2513.9(5) Å3, Z = 2) and Bu4N[Ni(dsise)2] (space group C2/c, a = 25.133(6) Å, b = 9.828(4) Å, c = 18.104(7) Å, β = 132.81(1)°, V = 3281(2) Å3, Z = 4) are given. 相似文献
13.
Antonio Gerson Bernardo da Cruz 《Thermochimica Acta》2006,443(2):217-224
Thermal properties and thermal decompositions of [NEt4]2[M(dmit)2] (M = Ni(II), Pd(II), dmit = 1,3-dithiole-2-thione-4,5-dithiolate) have been studied by thermogravimetry (TG). The TG analysis has shown that the complexes are thermally stable up to 460 K and the decomposition of the complexes occurs in three consecutive stages up to 873 K. A thermal stability scale for [M(dmit)2]n− anions was based on the thermal properties. Kinetics parameters, such as activation energy, Ea, and kinetic apparent pre-exponential factor, ln Aapp, have been calculated from the thermogravimetric data at heating rates of 10, 15, 20 and 25 K/min involving differential (Friedman's equation) and integral (Flynn-Wall-Ozawa's equation) methods. 相似文献
14.
Samar Eid 《Tetrahedron letters》2006,47(47):8333-8336
The first synthesis and X-ray structural determination of the bis(tetraethylammonium) Zn dithiolene complex involving N-methyl-1,3-thiazoline-2-thione-4,5-dithiolate, [NEt4]2[Zn(Me-thiazdt)2], are reported. The reactivity of this dithiolene complex as a nucleophilic dithiolate synthon and as a precursor of the air sensitive electron rich olefine, the bis ethylenedithiodithiadiazafulvalene (BEDT-DTDAF), is also described. 相似文献
15.
Ya. N. Kreitsberga R. S. Medne A. S. édzhinya M. V. Petrova O. Ya. Neiland 《Chemistry of Heterocyclic Compounds》1986,22(11):1186-1189
A method was developed for the preparation of bis(vinylenedithio)- and bis(dimethylvinylenedithio)tetrathiafulvalenes from 1,3-dithiole-2-thione-4,5-dithiolate.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 11, pp. 1470–1473, November, 1986. 相似文献
16.
EPR Studies on Oxovanadium(IV) Bis-Complexes of 1,2-Dithio Ligands EPR investigations on oxovanadium(IV) bis-complexes containing the ligands 1,3-dithiol-2-thione-4,5-dithiolate, dmit2?, 1,2-dithiol-3-thione-4,5-dithiolate, dmt2?, and 1,2-dithiooxalate are reported. The parameters of the spin-Hamiltonian are used to characterize the bonding properties, and are compared with those obtained for the corresponding VOS4 chelates containing four-membered chelate rings. According to this a successful characterization of VOS4 type mixed-ligand complexes should be possible. 相似文献
17.
《Polyhedron》1988,7(5):379-383
RhCl3·3H2O reacted with Na2dmit (dmit2−; 1,3-dithiole-2-thione-4,5-dithiolate anion) and [NBu4nOH in methanol to afford [NBu4n][Rh(dmit)2] (1) and [NBu4n]1.5[Rh(dmit)2] (2). Salt 1 was oxidized electrochemically in acetonitrile to afford [NBu4n]0.4[Rh(dmit)2] (3). Suspended powders of 1 or 2 reacted with iodine in hexane to afford [NBu4n][Rh(dmit)2][I3]1.3 (4) or [NBu4n]1.5[Rh(dmit)2[I3]0.4 (5). On the other hand, 1 dissolved in acetonitrile, reacted with bromine and iodine to yield [NBu4n]0.25[Rh(dmit)2Br] (6) and [NBu4n]0.35[Rh(dmit)2I] (7), respectively. All the salts behave as semi-conductors with electrical conductivities of 1 x (10−5 − 10−8) S cm−1 at 25°C measured for compacted pellets. Electronic absorption, ESR and X-ray photoelectron spectra of the salts are discussed. 相似文献
18.
《Journal of Coordination Chemistry》2012,65(5):768-775
A new copper complex of dmit, hexadecyltrimethylammonium bis(2-thioxo-1,3-dithiole-4,5-dithiolato)-copper([C16H33(CH3)3N][Cu(dmit)2], abbreviated as CTCU, C16H33(CH3)3N = hexadecyltrimethylammonium, dmit = 2-thioxo-1,3-dithiole-4,5-dithiolate) has been synthesized and its structure determined by X-ray diffraction. The saturable absorption of CTCU at 1053 nm shows promise as a Q-switch dye in the near IR regions. 相似文献
19.
《Analytical letters》2012,45(14):2727-2742
Abstract This report describes an attempt to develop potentiometric Mg2+ sensors based on a liquid polymeric membrane. Membrane incorporating 4,5-Bis(benzoylthio)-1,3- dithiole-2-thione (Bz2dmit) as ionophore, with composition Bz2 dmit:NaTPB:NB:PVC in the ratio 2.5:2.5:65:30 (w/w), exhibits the best result for potentiometric sensing of Mg2+ ions. The proposed electrode, based on Bz2 dmitwith nitrobenzene (NB) as a solvent mediator in a polyvinyl chloride (PVC) membrane matrix, exhibited a near-Nernstian response to Mg2+ in the concentration range of 1.0 × 10?5 to 1.0 × 10?1 M, with a slope of 29.2 mV per decade of activity of Mg2+. The lower limit of detection was 1.0 × 10?5 M. This sensor showed high selectivity with respect to alkaline, alkaline earth, transition, and heavy metal ions, except for Sr2+, and could be used over a pH range of 3.5–9.0. It can be used for at least 2 mo without considerable divergence in potentials and has a relatively fast response of <10 s. It was applied successfully as an indicator electrode in potentiometric titration of Mg2+ ions with EDTA. 相似文献
20.
A. M. A. Alaghaz 《Phosphorus, sulfur, and silicon and the related elements》2013,188(11):2807-2826
Novel [1,3-di-[N 1 -4-methoxy-1,2,5-thiadiazole-3-yl-sulfanilamide(sulfametrole)]-2″4-bis-[1,3-dithiole-2-thione-4,5-dithiolate]-2′,4′-dichl-orocyclodiphosph(V)azane] (III) , was prepared and their coordinating behavior towards the metal ions Co(II), Ni(II), Cu(II), and Pd(II) was studied. The structures of the isolated products are proposed based on elemental analyses, IR, UV, 1 H, and 31 P NMR, ESR, magnetic susceptibility, molar ratio, conductometric titration and electrical conductivity measurements. The prepared complexes showed high to moderate bactericidal activity compared with the ligand. 相似文献