Assembly of a supramolecular cube, [(Cp*WS3Cu3)8 Cl8(CN)12Li4] from a preformed incomplete cubane-like compound [PPh4][Cp*WS3(CuCN)3

A supramolecular cube has been formed by linking WS3Cu3 clusters with bidentate ligands. Eight WS3Cu3 clusters, which have an incomplete cubane-like structure, serve as the three connecting nodes of the cube, while 12 bridging cyanide anions coordinated to copper centers lie along the edges of the cube. Eight chloride anions and four lithium cations are located inside the cube.     

Mo(W)/Cu/S cluster-based supramolecular arrays assembled from preformed clusters [Et4N]4[WS4Cu4I6] and [(n-Bu)4N]2[MoOS3Cu3X3] (X = I, SCN) with flexible ditopic ligands

In our working toward the rational design and synthesis of cluster-based supramolecular architectures, a set of new [WS4Cu4]- or [MoOS3Cu3]-based supramolecular assemblies have been prepared from reactions of preformed cluster compounds [Et4N]4[WS4Cu4I6] (1) and [(n-Bu)4N]2[MoOS3Cu3X3] (2, X = I; 3, X = SCN) with flexible ditopic ligands such as dipyridylsulfide (dps), dipyridyl disulfide (dpds), and their combinations with dicyanamide (dca) anion and 4,4'-bipy. The cluster precursor 1 reacted with dps or dpds and sodium dicyanamide (dca) in MeCN to produce [WS4Cu4I2(dps)3].2MeCN (4.2MeCN) and [WS4Cu4(dca)2(dpds)2].Et2O.2MeCN (5.Et2O.2MeCN), respectively. On the other hand, treatment of 2 with dpds in DMF/MeCN afforded [MoOS3Cu3I(dpds)2].0.5DMF.2(MeCN)0.5 (6.0.5DMF.2(MeCN)0.5) while reaction of 3 with sodium dicyanamide (dca) and 4,4'-bipy in DMF/MeCN gave rise to [MoOS3Cu3(dca)(4,4'-bipy)1.5].DMF.MeCN (7.DMF.MeCN). Compounds 4.2MeCN, 5.Et2O.2MeCN, 6.0.5DMF.2(MeCN)0.5, and 7.DMF.MeCN have been characterized by elemental analysis, IR spectroscopy, and single-crystal X-ray crystallography. Compound 4 contains a 2D layer array made of the saddle-shaped [WS4Cu4] cores interlinked by three pairs of Cu-dps-Cu bridges. Compound 5 has another 2D layer structure in which the [WS4Cu4] cores are held together by four pairs of Cu-dca-Cu and Cu-dpds-Cu bridges. Compound 6 displays a 1D spiral chain structure built of the nido-like [MoOS3Cu3] cores via two pairs of Cu-dpds-Cu bridges. Compound 7 consists of a 2D staircase network in which each [MoOS3Cu3(4,4'-bipy]2 dimeric unit interconnects with four other equivalent units by a pair of 4,4'-bipy ligands and two pairs of dca anions. The [WS4Cu4] core in 4 or 5 and the [MoS3Cu3] core in 7 show a planar 4-connecting node and a seesaw-shaped 4-connecting node, respectively, which are unprecedented in cluster-based supramolecular compounds. The successful assembly of 4-7 from the three cluster precursors 1-3 through flexible ditopic ligands provides new routes to the rational design and construction of complicated cluster-based supramolecular arrays.     

Construction of [(eta5-C5Me5)WS3Cu3]-based supramolecular compounds from preformed incomplete cubane-like clusters [PPh4][(eta5-C5Me5)WS3(CuX)3] (X = CN, Br)

Approaches to the assembly of (eta5-C5Me5)WS3Cu3-based supramolecular compounds from two preformed incomplete cubane-like clusters [PPh4][(eta5-C5Me5)WS3(CuX)3] (X = CN, 1a; X = Br, 1b) have been investigated. Treatment of 1a with LiBr/1,4-pyrazine (1,4-pyz), pyridine (py), LiCl/py, or 4,4'-bipyridine (4,4'-bipy) and treatment of 1b with 4,4'-bipy gave rise to a new set of W/Cu/S cluster-based compounds, [Li[((eta5-C5Me5)WS3Cu3(mu3-Br))2(mu-CN)3].C6H6]infinity (2), [(eta5-C5Me5)WS3Cu3(mu-CN)2(py)]infinity (3), [[PPh4][(eta5-C5Me5)WS3Cu3(mu3-Cl)(mu-CN)(CN)].py]infinity (4), [PPh4]2[(eta5-C5Me5)WS3Cu3(CN)2]2(mu-CN)2.(4,4'-bipy) (5), and [[(eta5-C5Me5)WS3Cu3Br(mu-Br)(4,4'-bipy)].Et2O]infinity (6). The structures of 2-6 have been characterized by elemental analysis, IR spectra, and single-crystal X-ray crystallography. Compound 2 displays a 1D ladder-shaped chain structure built of square-like [[(eta5-C5Me5)WS3Cu3(mu3-Br)(mu-CN)]4](mu-CN)2(2-) anions via two pairs of Cu-mu-CN-Cu bridges. Compound 3 consists of a single 3D diamond-like network in which each (eta5-C5Me5)WS3Cu3 unit, serving as a tetrahedral node, interconnects with four other nearby units through Cu-mu-CN-Cu bridges. Compound 4 contains a 1D zigzag chain array made of cubane-like [(eta5-C5Me5)WS3Cu3(mu3-Cl)(mu-CN)(CN)]- anions linked by a couple of Cu-mu-CN-Cu bridges. Compound 5 contains a dimeric structure in which the two incomplete cubane-like [(eta5-C5Me5)WS3(CuCN)2(mu-CN)]- anions are strongly held together via a pair of Cu-mu-CN-Cu bridges. Compound 6 contains a 2D brick-wall layer structure in which dimers of [(eta5-C5Me5)WS3Cu3Br(4,4'-bipy)]2 are interconnected via four Cu-mu-Br-Cu bridges. The successful construction of (eta5-C5Me5)WS3Cu3-based supramolecular compounds 2-6 from the geometry-fixed clusters 1a and 1b may expand the scope of the rational design and construction of cluster-based supramolecular assemblies.     

Solid state synthesis of copper(I) thiotungstate cluster compounds at low heating temperatures. Crystal structures of [(n-Bu)4N]3-[WS4Cu3Cl3Br] and [Et4N]4[WS4Cu4I6]

Summary Reaction of [NH₄]₂[WS₄] with CuX (X = Cl or I) and R₄NX (R = Et or n-Bu) in the solid state gave two new bimetallic compounds with W:Cu compositions from 1:3 to 1:4. Compound (1), [(n-Bu)₄N]₃[WS₄Cu₃Cl₃Br], crystallizes in the hexagonal space group R3c with a = 17.051(5), c = 38.372(5) Å, V = 9661.8 ų, Z = 6. The cluster anion of (1) comprises a cubane-like cluster core [WS₃Cu₃Br] of C₃ symmetry with a Cl atom attached to each of the three Cu atoms and one terminal sulphido ligand attached to the W atom. Compound (2), [Et₄N]₄[WS₄Cu₄I₆], crystallizes in the monoclinic space group C2/m with a = 29.702(6), b = 12.7887(5), c = 15.327(3)Å, = 99.69(2), V = 5738.1 ų, Z = 4. In the cluster anion of (2), four edges of the WS₄ core are coordinated by four Cu atoms, giving a WS₄Cu₄ aggregate of approximate C_2V symmetry.     

钼(钨)/铜/硫三核簇合物[A]2[MS4(CuCN)2] (M=Mo,W;A=Et4N,PPh4)的合成及晶体结构

合成了四个三核簇合物[A]2[MS4(CuCN)2](1A＝Et4N,M＝Mo;2A＝PPh4,M＝W;3A＝Et4N,M＝W;4A＝PPh4,M＝Mo),测定了[Et4N]2[MoS4(CuCN)2]*H2O(1*H2O)和[PPh4]2[WS4(CuCN)2]*0.5DMF*H2O(2*0.5DMF*H2O)的晶体结构.1和2的簇阴离子[MS4(CuCN)2]2-(M＝Mo,W)均具有一个双齿配体MS42-和两个CuCN形成的近似D2d对称性结构.     

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.     

The Binary Group 4 Azides [PPh4]2[Zr(N3)6] and [PPh4]2[Hf(N3)6]

The binary zirconium and hafnium polyazides [PPh₄]₂[M(N₃)₆] (M=Zr, Hf) were obtained in near quantitative yields from the corresponding metal fluorides MF₄ by fluoride–azide exchange reactions with Me₃SiN₃ in the presence of two equivalents of [PPh₄][N₃]. The novel polyazido compounds were characterized by their vibrational spectra and their X‐ray crystal structures. Both anion structures provide experimental evidence for near‐linear M‐N‐N coordination of metal azides. The species [M(N₃)₄], [M(N₃)₅]^? and [M(N₃)₆]^2? (M=Ti, Zr, Hf) were studied by quantum chemical calculations at the electronic structure density functional theory and MP2 levels.     

Construction of new heteroselenometallic clusters: formation of crownlike [Et4N]4[(mu5-WSe4)(CuI)5(mu-I)2] and octahedral polymeric [(mu6-WSe4)Cu6I4(py)4]n from planar [Et4N]4[(mu4-WSe4)Cu4I6] with additional faces

The coplanar cluster compound [Et4N]4[(mu4-WSe4)Cu4I6] (1) was prepared from reaction of [Et4N]2[WSe4] with 4 equiv of CuI in N,N-dimethylformamide (DMF) solution in the presence of [Et(4)N]I. Treatment of 1 with pyridine (py) in dry MeCN gave the neutral cluster [(mu4-WSe4)Cu4(py)6I2] (2) in good yield. Recrystallization of 1 from py/i-PrOH resulted in the reorganization of the coplanar WSe4Cu4 core and the formation of a neutral polymeric cluster [(mu3-WOSe3)Cu3(py)3(mu-I)]n (3) containing a nest-shaped OWSe3Cu3 core and a terminal W=O bond. The interaction of cluster 1 with excess PPh3 in CH3Cl3 gave [(mu3-WSe4)Cu3(PPh3)3(mu3-I)] (4) which has a cubanelike SeWSe3Cu3I core. Treatment of 1 with 1 equiv of CuI in dimethyl sulfoxide (DMSO) yielded [Et4N]4[(mu5-WSe4)(CuI)5(mu-I)2] (5) which has a crown-like core structure. Treatment of 1 in DMF with 2 equiv of CuI in the presence of py resulted in the formation of a two-dimensional polymeric cluster, [(mu6-WSe4)Cu6I4(py)4]n (6), consisting of an octahedral WSe4Cu6 repeating unit. The solid-state structures of clusters 3, 5, and 6 have been further established by X-ray crystallography. The nonlinear optical properties of 6 have been also investigated. Cluster 6 was found to exhibit good photostability and a large optical limiting effect with the limiting threshold being ca. 0.3 J cm(-2).     

Construction of symmetric and asymmetric Mo/S/Cu clusters from a cluster precursor [Et4N]2[(edt)2Mo2S2(mu-S)2] (edt = ethanedithiolate)

Treatment of [Et 4N] 2[(edt) 2Mo 2S 2(mu-S) 2] ( 1) (edt = ethanedithiolate) with equimolar CuBr afforded an anionic hexanuclear cluster [Et 4N] 2[(edt) 2Mo 2(mu-S) 3(mu 3-S)Cu] 2.2CH 2Cl 2 ( 2.2CH 2Cl 2). On the other hand, reactions of 1 with 2 equiv of CuBr in the presence of 1,2-bis(diphenylphosphino)methane (dppm) and pyridine (Py) ligands gave rise to two neutral tetranuclear clusters [(edt) 2Mo 2O 2(mu-S) 2Cu 2(dppm) 2] ( 3) and [(edt) 2Mo 2O(mu 3-S)(mu-S) 2Cu 2(Py) 4] ( 4), respectively. The reaction of 1 with 2 equiv of CuBr followed by the addition of a mixture of dppm and Py (molar ratio = 1:2) yielded another neutral tetranuclear cluster [(edt) 2Mo 2(mu-S) 2(mu 3-S) 2Cu 2(dppm)(Py)].Py ( 5.Py). Compounds 2- 5 have been characterized by elemental analysis, UV-vis spectra, IR spectra, (1)H NMR, and X-ray analysis. The structure of the dianion of 2 can be viewed as having a [Mo 4S 8Cu 2] core in which two chemically equivalent [Mo 2(mu-S) 3(mu 3-S)(edt) 2Cu] (-) anions are linked by two extra Cu-S edt bonds. The molecular structure of 3 may be visualized as being built of one [(edt) 2Mo 2X 2(mu-S) 2] (2-) dianion and one [Cu 2(dppm) 2] (2+) dication that are connected by a pair of M-mu-S edt bonds. Compound 4 is formed by the affiliation of two Cu(I) atoms only at one end of the [(edt) 2Mo 2S 2(mu-S) 2] moiety, connecting with the S t atoms and the S edt atom. Cluster 5.Py can be viewed as being constructed from the addition of one Cu atom onto the incomplete cubanelike [Mo 2S 4Cu] framework through one terminal sulfur and one edt sulfur. Among the four clusters, 3 and 4 have internal mirror symmetry or pseudo mirror symmetry, respectively, while 2 and 5 are asymmetric clusters with racemic formation.     

Synthese und Kristallstruktur von [N(Hex)4][Cu2(CN)3]

Synthesis and Crystal Structure of [N(Hex)₄] [Cu₂(CN)₃] [N(Hex)₄][Cu₂(CN)₃] has been prepared by solvothermal reaction of CuCN with Tetra‐n‐hexylammoniumiodide in acetone. The crystal structure is built up by condensed (CuCN)₆ and (CuCN)₇ rings, forming a zeolith type cyanocuprate(I) framework [Cu₂(CN)₃^—]. Space group R3; α = 44.482(6), c = 21.283(4) Å, V = 36471(9) ų; Z = 9.     

Azidocuprate(II). Die Kristallstruktur von (PPh4)2[Cu2(N3)6]

Azidocuprates(II). Crystal Structure of (PPh₄)₂[Cu₂(N₃)₆] (PPh₄)₂[Cu(N₃)₄] and (PPh₄)₂[Cu₂(N₃)₆], which is already known, are prepared from the corresponding chloro cuprates and excess silver azide in dichloro methane suspension. The azido cuprates form nonexplosive brown crystals of low sensitivity to moisture and are characterized by i.r. spectroscopy. (PPh₄)₂[Cu₂(N₃)₆] was submitted to a X-ray crystallographic structural analysis (4284 observed, independent reflexions, R = 0.034). The compound crystallizes triclinic in the space group P1 with one formula unit per unit cell. The lattice parameters are a = 1047.4 pm; b = 1131.1 pm; c = 1179.4 pm; α = 101.26°; β = 109.31°; γ = 103.42°. The compound consists of PPh₄^⊕ cations and centrosymmetric anions [Cu₂(N₃)₆]^2?, which meet D_2h-symmetry fairly well. In the anions the copper atoms are linked to a planar Cu₂N₂ four-membered ring by the N α atoms of two azide groups. The other azido ligands are bonded terminally and complete coordination number 4 at the Cu atoms which show planar geometry.     

A heteropolynuclear R2[S2WS2Re(O)(Cl)S2WS2] (R = PPh4 and Et4N) complex. The first example of a tetrathiometalate ligand co-ordinated to an oxo-metal core

A solution of [ReOCl3(PPh3)2] in benzene reacts with solid (NH4)2WS4, in the presence of traces of H2O, to give [ReOCl(WS4)2]2–, isolated as its PPh4 (1) and NEt4 (2) salts. Both (1) and (2) exhibit (Re=O) at ca. 930, (Re=Cl) at ca. 330 (W=S)t at ca. 495 and (W–S–Re) bridging vibration at ca. 460cm–1. The FAB mass spectrum of (1) shows a peak for [ReO(WS4)2]+(m/z=826 amu) in the positive mode and that for PPh4[ReOCl(WS4)]– (m/z=889amu) in the negative mode, confirming the suggested composition. This is the second example of a d2 metal ion forming a tetrathiometalate complex and also the first example of an oxometal ion (excepting those of W and Mo) forming a molecular complex with tetrathio- tungstate or -molybdate ligands.     

Crystal Structures of (PPh3)2Pd(N3)2, (AsPh3)2Pd(N3)2, (2‐Chloropyridine)2Pd(N3)2, [(AsPh4)2][Pd2(N3)4Cl2], [(PNP)2][Pd(N3)4], [(AsPh4)2][Pt(N3)4] · 2 H2O,and [(AsPh4)2][Pt(N3)6]

The crystal structures of the monomeric palladium(II) azide complexes of the type L₂Pd(N₃)₂ (L = PPh₃ ( 1 ), AsPh₃ ( 2 ), and 2‐chloropyridine ( 3 )), the dimeric [(AsPh₄)₂][Pd₂(N₃)₄Cl₂] ( 4 ), the homoleptic azido palladate [(PNP)₂][Pd(N₃)₄] ( 5 ) and the homoleptic azido platinates [(AsPh₄)₂][Pt(N₃)₄] · 2 H₂O ( 6 ) and [(AsPh₄)₂][Pt(N₃)₆] ( 7 ) were determined by X‐ray diffraction at single crystals. 1 and 2 are isotypic and crystallize in the triclinic space group P1. 1 , 2 and 3 show terminal azide ligands in trans position. In 4 the [Pd₂(N₃)₄Cl₂]^2– anions show end‐on bridging azide groups as well as terminal chlorine atoms and azide ligands. The anions in 5 and 6 show azide ligands in equal positions with almost local C_4h symmetry at the platinum and palladium atom respectively. The metal atoms show a planar surrounding. The [Pt(N₃)₆]^2– anions in 7 are centrosymmetric (idealized S₆ symmetry) with an octahedral surrounding of six nitrogen atoms at the platinum centers.     

从固相反应产物[NEt4]4[Mo2O2S6Cu6I4Br2]合成原子簇[MoOS3Cu3I(3,5-diMePy)4]·CH3CN和(EtN)4[Mo4Cu8O4S12{(Ph2PS)2}4](英文)

Treatment of iodide-bridged dimer [NEt4] 4[Mo2O2S6Cu6I4Br2] 1 with 3, 5-bimethylpyridine or with K[(Ph2PS) 2N] in CH3CN afforded the tetranuclear cluster [MoOS3Cu3I(3,5-diMePy)4]·CH3CN 2 and dodecanuclear cluster (Et4N)4[Mo4Cu8O4S12{(Ph2PS)2N}4] 3. Monomeric 2 possess a nest-shaped skeleton.The structure of oligomeric 3 can be regarded as a tetramer of nest-shaped MoCu3OS3[(Ph2PS)aN]groups co-polymerized by sharing the limbic Cu atoms.     

Reaktionsprodukte von S7NH mit Nickel- und Kupfersalzen Darstellung und Struktur der Komplexe [(CH3)4N][Ni(S3N)(CN)2], [(C6H5)4As][Cu(S3N)2] und [(C6H5)4As][Cu(S3N)CI]

Metal Sulfur Nitrogen Compounds 18. Reaction Products of S₇NH with Nickel and Copper Salts. Preparation and Structures of the Complexes [Ch₃₄N][Ni(S₃N)(CN)₂], [(C₆H₅)₄As][Cu(S₃N)₂], and [(C₆H₅)₄AS][Cu(S₃N)Cl]. In the presence of MOH (M = K, [(CH₃)₄N]), S₇NH reacts with Ni(CN)₂ to yield, besides the three-nuclear complex M[(S₃NNi)₃S₂], the new mononuclear complex M[Ni(S₃N)(CN)₂]. The [(CH₃)₄N]⁺ salt is monoclinic, C2/m, a = 19.303(9), b =6.941(3), c=16.309(10) Å, β = 144.51⁰(2), Z = 4. The [Ni(S₃N)(CN)₂]- anion is planar, Ni being coordinated by one S₃N^? chelate ligand and by two CN^? ions. From the reaction of CuCI₂, S₇NH, and [Ph₄As]OH result the salts [Ph₄As][Cu(S₃N)₂] or [Ph₄As][Cu(S₃N)Cl], depending on the reaction conditions. [Ph₄As][Cu(S₃N)₂] is triclinic, P&1macr;, a = 7.073(3), b = 11.742(4), c = 16.439(6) Å α = 91.08°(3), β = 99.01°(3), γ = 91.58°(3), Z = 2. Two S₃N^? chelate ligands coordinate to Cu^I in a distorted tetrahedral arrangement. [Ph₄As][Cu(S₃N)Cl] is monoclinic, C2/c, a = 17.174(6), b = 13.650(5), c = 21.783(5) Å β = 100.45°(2), Z = 8. Cu^I is coordinated by one S₃N^? chelate ligand and one C1^?, resulting in a trigonal planar environment.     

A mixed-valence coordination polymer featuring two-dimensional ferroelectric order: {[Cu(I)4Cu(II)(Et2dtc)2Cl3][Cu(II)(Et2dtc)2]2(FeCl4)}n (Et2dtc- = diethyldithiocarbamate)

The first mixed-valence coordination polymer indicating ferroelectric properties, {[CuI4CuII(Et2dtc)2Cl3][CuII(Et2dtc)2]2(FeCl4)}n (Et2dtc- = diethyldithiocarbamate), has been synthesized and crystallographically characterized. This complex has a two-dimensional infinite square lattice structure, including both Cu(I) and Cu(II) ions, which is confirmed by XPS and SQUID measurements. In addition, the ferroelectric behaviors are revealed by the dielectric measurements with a LCR meter and a ferroelectric tester.     

The first examples of metal-mediated addition of a phosphorus imine to nitriles; the preparation and X-ray crystal structures of [PtCl4{NH=C(Et)N=PPh3}2] and [PtCl2(EtCN){NH=C(Et)N[double bond, length as m-dash]PPh3}

Imino(triphenyl)phosphorane, Ph3P=NH (1), reacts with nitrile complexes of Pt(IV) to generate hydrolytically sensitive [PtCl4{NH=C(R)N=PPh3}2](R=Me 2a, Et 2b, Ph 2c), and with the Pt(II) complex [PtCl2(EtCN)2] to give [PtCl2(EtCN){NH=C(Et)N=PPh3}](3) and [PtCl2{NH=C(Et)N=PPh3}2](4); X-ray crystallography performed upon (2b) and (3) confirms the presence of an imine/nitrile addition ligand bound by the terminal nitrogen.