Syntheses and Characterization of Two Novel Mo（W）/Cu/S Dodecanuclear Clusters with Triple Incomplete Cubane-like Structure

The self-assembly reactions of [MOS3]^2- （M = W, Mo） with CuS2COCH3 in DMF produced two novel dodecanuclear Mo（W）/Cu/S heterometallic clusters, [Et4N]4[{MOS3}3Cu6S2- （CuS2COCH3）3]·H2O （1： M = W; 2： M = Mo）. Cluster 1 crystallizes in hexagonal, space group P-62c with a = 16.5612（3）, b = 16.5612（3）, c = 16.4660（5）A, Z = 2, V = 3911.13（16）A^3, Dc = 1.935 g/cm^3, μ（MoKα） = 7.269 mm^-1, F（000） = 2192, the final R = 0.0289 and wR = 0.0789 for 2425 observed reflections （I 〉 2σ（I））. Cluster 2 is isomorphous to 1 with similar crystal parameters. X-ray analysis reveals that both clusters consist of three incomplete cubane-like cluster units {MOS3Cu3S2COCH3}, which are linked together by two μ3-S atoms.     

Synthesis and Crystal Structures of Four Novel Mo(W)/Cu/S Polymers Containing Thiolato Bridging Ligands

Four novel M/Cu/S polymers [Et₄N][MS₄Cu₃(S₂COEt)₂] (1a: M=Mo; 1b: M=W) and Et₄N][MS₄Cu₂SEt] (2a: M=Mo; 2b: M=W) have been prepared by reactions of [Et₄N]₂[MS₄] with CuS₂COEt and CuSEt. X-ray crystal structure determinations reveal that the polymeric anions of complexes 1a and 1b both consist of MS₄Cu₃ building blocks linked via bidentate [S₂COEt]⁻ bridging ligands to form 1D polymeric chains. The anion structures of the polymeric compounds 2a and 2b contain MS₄Cu₂ repeating units which are connected via μ-SEt⁻ ligands forming a zigzag chain running down the crystallographic b axis.     

Assembly of molecular squares and helical chain polymers of Mo(W)/Cu/S clusters using thiolato ligands as linkers

Reactions between thiomolybdate or thiotungstate [Et₄N]₂[MS₄] (M = Mo, W) and CuSBu^t led to the formation of two novel Mo(W)/Cu/S clusters [Et₄N]₄[{MS₄Cu₂(μ-SBu^t)}₄] (1, M = Mo; 2, M = W). Single-crystal X-ray diffraction studies reveal that 2 is the first example of a molecular square containing CuS₂WS₂Cu building blocks. The reactions of [Et₄N]₂[MS₄] with CuCl followed by the addition of K₂SSS (SSS = 1,3,4-thiadiazole-2,5-dithiolate) yielded novel polymers {[Et₄N]₂[MS₄Cu₂(SSS)]}_n (3, M = Mo; 4, M = W). Crystal structure determination shows that the CuS₂WS₂Cu building blocks in the anion of 4 are bridged by SSS²⁻ ligands to produce a helical chain running down the crystallographic b axis.     

新颖五核Mo/Cu/S簇合物[MoOS3Cu4(α-MePy)6Br2]的合成及晶体结构

杂核金属含硫簇合物具有丰富的结构,在生物化学、催化和非线性光学等方面显示了诱人的应用前景.近年来,我们主要从事用[MS4 ]2 - 和[Cp* MS3]- ( M=Mo,W)和Cu( ) ,Ag( )反应合成Mo( W) /Cu( Ag) /S簇合物并研究其非线性光学性质[1,2 ] .鉴于用硫代金属酸盐作前驱体合成M- Cu- Ag- S杂三核金属簇合物的工作鲜有报道[3] ,我们尝试用( NH4 ) 2 Mo OS3和Cu Br,Ag Br在α- Me Py中反应,希望得到Mo- Cu- Ag- S杂三核金属簇合物.但上述反应却形成了1个仅含Mo和Cu( )的五核簇合物[Mo OS3Cu4 (α- Me Py) 6 Br2 ],其所含的Mo S3…     

Heterobimetallic Cluster-Based Coordination Polymers: Assembly,Structures and Third-Order Nonlinear Optical Properties

Reactions of (NH₄)₂WS₄ with CuCN, CuCN/1,2-bis(4-pyridyl)propane (bppa) or [Cu(MeCN)₄]PF₆/bppa under different reaction conditions afforded a set of two- or three-dimensional W/Cu/S cluster-based coordination polymers including {[Et₄N]₂[WS₄Cu₄(μ-CN)₂(μ-I)₂]}_n ( 1 ), [WS₄Cu₄(μ-CN)₂(bppa)₂]_n ( 2 ) and {[WS₄Cu₄(bppa)₄](PF₆)₂}_n ( 3 ), respectively. Compound 2 can be readily formed from reaction of 1 with bppa under solvothermal conditions. Compounds 1 and 2 feature two-dimensional networks with a “sql” topology, while 3 possesses a two-fold interpenetrated three-dimensional net with a rare “reo” topology. Compounds 1 – 3 in DMF exhibited different third-order nonlinear optical responses, and they all showed a reverse saturable absorption while 2 held a strong self-focusing effect.     

TA on Mo(W)/Cu(Ag)/S clusters derived with [Cp*MS3]- Kinetics of [PPh4]2[Cp*WS3(CuBr)3]2 and [PPh4]2[Cp*MoS3(CuBr)3]2

Thermal analysis on two new heterometallic sulfide clusters, [PPh4]2[WS3(CuBr)3]2 and [PPh4]2[MoS3(CuBr)3]2 (where PPh4=tetraphenyl phosphonium, =pentamethylcyclopenta- dienyl), was carried out using a simultaneous TG-DTA unit in an atmosphere of flowing nitrogen and at various heating rates. Supplemented using EDS method, their thermal behavior and properties, together with the composition of their intermediate product, were examined and discussed in connection with their distinctive molecular structure as a dianion, which provided some theoretically and practically significant information. Both clusters decomposed in a two-step mode, but without a stable new phase composed of Mo/W-Cu-S formed during their decomposition process as we expected. Based on TG-DTG data, four methods, i.e. Achar-Brindley-Sharp, Coats-Redfern, Kissinger and Flynn- Wall-Ozawa equation, were used to calculate the non-isothermal kinetic parameters and to determine the most probable mechanisms. This revised version was published online in July 2006 with corrections to the Cover Date.     

Hydrothermal Synthesis and Crystal Structure of a New 2D Zinc（Ⅱ） Coordination Polymer with 2-Aminoethanesulfonic Acid

A new 2D Zn(Ⅱ) coordination polymer [Zn(TAU)2]n (1, HTAU=2-aminoethane- sulfonic acid) constructed by 2-aminoethanesulfonic acid ligand has been hydrothermally synthesized by the reaction of Zn(CH3COO)2 and 2-aminoethanesulfonic acid with a 1:2 mole ratio and characterized by single-crystal X-ray diffraction, elemental analysis, infrared spectroscopy and thermogravimetric analysis. Crystal structural analysis reveals it crystallizes in monoclinic, space group P21/c with a=8.672(4), b=6.523(3), c=9.134(5) , β=115.441(5)°, V=466.6(4) 3, Mr=313.65, Z=2, Dc=2.232 Mg·m-3, F(000) =320, μ(MoKα)=3.091 mm-1, the final R=0.0358 and wR=0.0919 for 2026 observed reflections with Ⅰ > 2σ(Ⅰ). In the structure, each zinc(Ⅱ) ion is coordinated in a slightly distorted octahedron, and each μ3-TAU– acts as a bridge to bond three neighboring Zn(Ⅱ) ions to form an infinite 2D network structure.     

两个含[MS4Cu4]簇核的一维配位聚合物{[MS4Cu4(bpe)2(ani)2I2]·3.5ani}n(M=Mo,W;ani=苯胺)的组装及其晶体结构

前驱团簇[Et₄N]₄[MS₄Cu₄I₆](M=Mo(1a);W(1b))与双齿桥连配体1,2-双(4-吡啶基)乙烷(bpe)在苯胺溶液中反应,生成2个结构相似的一维[MS₄Cu₄]团簇基配位聚合物{[MS₄Cu₄(bpe)₂(ani)₂I₂]·3.5ani}_n(M=Mo(2),W(3);ani=苯胺)。通过元素分析、红外光谱和X-射线单晶衍射对2和3进行了表征。晶体结构分析表明前驱团簇1a和1b中五核马鞍形[MS₄Cu₄]簇核分别在2和3中得以保留,2个桥连配体bpe连接相邻的簇核,在[111]方向延伸形成一维"Z"字形链结构。     

两个含[MS4Cu4]簇核的一维配位聚合物{[MS4Cu4(bpe)2(ani)2I2]·3.5ani}n (M=Mo, W; ani=苯胺)的组装及其晶体结构

前驱团簇[Et₄N]₄[MS₄Cu₄I₆](M=Mo (1a); W (1b))与双齿桥连配体1, 2-双(4-吡啶基)乙烷(bpe)在苯胺溶液中反应, 生成2个结构相似的一维[MS₄Cu₄]团簇基配位聚合物{[MS₄Cu₄(bpe)₂(ani)₂I₂]·3.5ani}_n (M=Mo (2), W (3); ani=苯胺)。通过元素分析、红外光谱和X-射线单晶衍射对2和3进行了表征。晶体结构分析表明前驱团簇1a和1b中五核马鞍形[MS₄Cu₄]簇核分别在2和3中得以保留, 2个桥连配体bpe连接相邻的簇核, 在[111]方向延伸形成一维“Z”字形链结构。     

Synthesis of a new salt containing polyoxometallate anion and M?Cu?S cluster cation [MS4Cu4(γ-MePy)8][M6O19] (M = Mo,W). Crystal structure of [WS4Cu4(γ-MePy)8] [W6O19]

Reactions of (NH₄)₂MS₄, AgBr and CuBr in γ-methylpyridine produced one new compound, [MS₄Cu₄(γ-MePy)8][M₆O₁₉] (1, M = W; 2 , M = Mo), of which 1 was characterized by single crystal X-ray analysis. The crystal data: orthorhombic, Pbcn, a = 15.434(4), b = 16.732(2), c = 28.657(7) Å, V = 7400.8(8) ų, Z = 4 , R = 0.072 for 3121 independent data. The compound is the first example which contains both polyoxotungstate anion and heteropolynuclear cluster cation. In the structure of the cation four edges of the tetrahedral WS^2?₄ core are coordinated by four copper atoms, giving a WS₄Cu₄ aggregate of approximate D_2h symmetry. The differences between the reaction of Cu⁺ with MS^2?₄ and that of Ag+ with MS^2?₄ in pyridine and its derivatives are discussed.     

Crystal structure of tetraethylammonium bis(tetracarbonylmolybdenum)-tetrathiotungstate, [EtN][(OC)MoSWSMo(CO)] and synthesis, infrared spectra, 95 Mo NMR spectra and cyclic voltammetry of new linear trinuclear Mo(W)–S carbonyl clusters containing mixed-valence metal atoms [(OC)MSM′SM(CO)]− (M, M′=Mo or W)

Four trinuclear molybdenum(tungsten)-sulfur carbonyl cluster compounds, [Et₄N]₂[(OC)₄Mo-S₂MoS₂Mo(CO)₄] (1), [Et₄N]₂[(OC)₄WS₂WS₂W(CO)₄] (2), [Et₄N]₂[(OC)₄MoS₂WS₂Mo(CO)₄] (3), [Et₄N]₂[(OC)₄WS₂MoS₂W(CO)₄] (4) have been prepared by both reaction of [M(CO)₄(S₂CNEt₂)]⁻ with M′S₄²− in MeOH and reaction of MeCN solution of M(CO)₆ with M′S₄²− in MeOH (M=Mo, W; M′=Mo, W). These complexes has been characterized by routine elemental analysis and spectroscopy and the structures of 1 and 3 have been determined by X-ray crystallography. The structure study reveals that the anion of 3 contains a heteronuclear Mo–W–S trimetallic core, [MoS₂WS₂Mo]²−, consisting of two perpendicular rhombic MoS₂W units sharing a tungsten atom. The Mo–W bond distances are 3.028(2) and 3.031(2) Å and the Mo–W–Mo angle is 176.04(5)°. The average bond lengths of W–S and Mo–S are 2.21 and 2.54 Å, respectively. The X-ray, structure, IR, CV (cyclic voltammetry) and 95 Mo NMR studies on these four cluster complexes indicated that these cluster complexes possess wide separated oxidation states of metal atoms and exhibit the charge transfer, M^L→M^HS₄ (M^L represents a low-valance metal atom and M^H a high valence metal atom), between the two different valence metallic centers in the cluster complexes. It has been found that the charge transfer, M^L→M^HS₄, in the complexes are: 1>4, 3>2, 1>3, 4>2, 1>2 and 34 implying the electron-donation ability of low-valence metal atoms in the complexes is Mo⁰>W⁰ and the electron-accepted ability of the high valence metal atoms in the complexes is Mo^VI>W^VI.     

Syntheses, spectra and crystal structures of a series of Mo/S(O) complexes containing oxalate ligand

Two Mo/S complexes: K₆[Mo₂O₂S₂(C₂O₄)₂-(ClPO₃)₂]·H₂O (1) and K₆[Mo₂O₃S(C₂O₄)₂(ClPO₃)₂]·3H₂O (2) containing oxalate ligand were prepared by the reaction of (NH₄)₂MoS₄ and potassium oxalate by adding a small amount of H₃PO₄ to adjust the value of pH in the system of methanol and water under an atmosphere of pure nitrogen at ambient temperature and characterized by means of elemental analysis, IR, and UV-Vis. Results of the analysis reveal that crystals of the complex 1 are orthorhombic, space group Pbcn, a = 4.6370(2) nm, b = 0.7549(2) nm, c = 1.3888(4) nm, V = 4.861(2) nm³, Z = 8, M = 945.49, Dc = 2.58 g/cm³, μ = 2.625 cm⁻¹, R = 0.063, and wR = 0.075. In addition, their spectral properties were also discussed. Translated from Chem. Res. Appl., 2006, 18(4) (in Chinese)     

含有草酸配体的钼硫(氧)配合物的合成、光谱及晶体结构

草酸是重要的有机配体,它能和许多金属形成配合物,并具有不同的分子结构[。1-3]其中,钼与草酸形成的配合物研究一直是人们关注的焦点。主要有以下原因:1、钼与草酸形成的配合物在结构上形式多样,即使同一组成的配合物,也有不同结构。如K2[MoO3(C2O4)]·H2O[4],由于合成方法不同     

A New Dinuclear Cu(Ⅱ) Complex of a Ligand with Benzimidazole Group─Synthesis and Crystal Structure

A new dinuclear copper complex, [Cu(C9H11N3)Cl2]2 (C18H22Cl4Cu2N6), has been synthe- sized and characterized by X-ray structure determination. It crystallizes in the triclinic P1 space group with a = 7.526(3), b = 9.473(4), c = 9.535(3) , α = 117.214(10), β = 108.251(9), γ = 91.560(6)o, V = 562.3(4) 3, Z = 1, Mr = 591.30, F(000) = 298, Dc = 1.746 g/cm3, μ(MoKα) = 2.385 mm-1, the final R = 0.0577 and wR = 0.1248 for 2188 unique reflections with 1629 observed ones (I > 2σ(I)). In the title complex, each copper(II) atom is located at the center of a distorted trigonal bipyramid of five coordination atoms (two nitrogen and three chlorine atoms). Two copper(II) atoms were bridged by two chlorine anions (Cl(2) and Cl(2a)) to form a Cu(II)-Cu(II) binuclear entity with the distance between two copper(II) atoms of 3.398 .     

A 1D Cu(II) coordination polymer exhibiting ferromagnetic interactions and a mononuclear Cu(II) complex of substituted pyrazole carboxylic acids: Synthesis, characterization and crystal structure

Reaction of 2 equiv. amount of copper(II) nitrate hexahydrate with 1 equiv. of 5-methyl-1-pyridin-2-yl-1H-pyrazole-3-carboxylic acid (PyPzCA) in presence of triethyl amine base afforded a 1D coordination polymeric compound [Cu₂(PyPzCA)₂(H₂O)₃(NO₃)]NO₃·H₂O (1). Whereas, the same reaction when repeated with 1-(4,6-dimethyl-pyrimidin-2-yl)-5-methyl-1H-pyrazole-3-carboxylic acid (PymPzCA) instead of PyPzCA, a mononuclear compound [Cu(PymPzCA)]·2H₂O·NEt₃ (2) is formed. Both the complexes are crystallographically characterized. In 1, both the copper atoms (Cu1 and Cu2) have distorted square pyramidal geometry with N₂O₃ chromophore while, in 2, the central copper atom has a distorted trigonal bipyramidal geometry with N₄O chromophore. Complex 1, is a 1D coordination polymer where the metal centers being far apart and are involved in a weak ferromagnetic interaction which is quite unexpected.     

ChemInform Abstract: CuYS2: A Ternary Copper(I) Yttrium(III) Sulfide with Chains 1∞{ [Cu(S1)3/3(S2)1/1]3‐} of cis‐Edge Connected [CuS4]7‐ Tetrahedra.

ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.     

A comprehensive approach in perceiving the chelation of Cu(II) and Zn(II) with Alizarin Red S using pH-oscillotitrimetric and volumetric-oscillographic methods

In order to understand the chelation process and investigate the intermediate species as a step towards verifying the exact functional groups that are involved in bonding with transition metals, specifically Cu(II) and Zn(II), pH-oscillotitrimetric (pHOT) and volumetric-oscillographic (VOG) methods have been profoundly used. Alizarin Red S (ARS) - as one of the chameleon compounds (chromogenic) - confirms its different approach of bonding with copper and zinc in different mediums. These two methods thoroughly confirm the adequate conditions for each metal to chelate with ARS. pH is responsible for the ambience in which the formation energy in its less value for the salt or complex to be formed, confirming that pH  =  5 is the value that allows Cu(II) to bond with ARS, whereas Zn(II) bonds at pH = 6. A new approach has been also suggested as to how to discuss the titrimetric curves in both methods, taking into account the importance of ‘volumetric-oscillographs’ that give more information when analysed appropriately. Volumetric-oscillographs have been shown and utilized as fingerprint spectrums to track any change in the solutions and firmly expect the compounds that can be step-by-step formed during titration operation. The resulting-in rules have been suggested during reading the graphs. Moreover, the competition between these two metals to chelate with ARS has been extensively studied.     

ChemInform Abstract: Cu1.45Er0.85S2: A Copper(I) Erbium(III) Sulfide with Cation‐Deficient CaAl2Si2‐Type Structure.

ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.     

一维链状的3-羧基苯氧乙酸铜配位聚合物[Cu(3-cpoa)(phen)(H2O)]n的合成与晶体结构

A novel coordination polymer [Cu(3-cpoa)(phen)(H₂O)]_n(3-cpoa^2-=3-carboxylphenoxyacetate, phen=1,10-phenanthroline) was synthesized and characterized by elemental analysis, IR spectra and single crystal X-ray diffraction. Crystallographic facts are as follows: monoclinic crystal system, space group P2₁/n， a=0.688 96(14) nm， b=1.652 3(3) nm， c=1.651 1(3) nm， β=95.20(3)°, V=1.871 9(6) nm³, Z=4, D_c=1.618 g·cm^-3， F(000)=932， μ=1.211 mm^-1，R=0.048 2 and wR=0.062 2. The copper atom exhibits a distorted square pyramidal coordination geometry, involving two oxygen atoms of different 3-cpoa^2- ligands, two nitrogen atoms of 1,10-phen ligand and one coordinated water molecule. The copper atoms are bridged by 3-cpoa^2- ligand, forming a one-dimensional chain along c axis. The distance of adjacent Cu…Cu is 0.916 6(4) nm. A three-dimensional network structure is constructed by the intermolecular hydrogen bond and π-stacking interactions. CCDC: 219724.