A Novel Tantalum Cluster Chalcohalide Ta4S1.5Se7.5I8

Single crystals of Ta₄S_1.5Se_7.5I₈ are obtained by heating Ta, S, Se and I₂ at 300 °C in 4.0:1.0:8.0:4.4 molar ratio. The structure was determined by X-ray analysis and consists of molecular clusters [Ta₄(μ₄-S)(μ₂-Q_axSe_eq)₄I₈] (Q ≈ Se_0.87S_0.13). The tantalum atoms form a square with long Ta…Ta distances (3.26–3.32 Å), with four dichalcogenide ligands bridging the Ta–Ta edges and a sulfur atom capping the square. Each Ta atom has two terminal iodine atoms. Raman spectroscopy study shows the presence of the characteristic absorption band at 396 cm^?1 which is due to the Ta₄–μ₄-S vibrations. Cyclic voltammetry shows that Ta₄S_1.5Se_7.5I₈ in solid state undergoes quasi-reversible one-electron oxidation which is metal-centered.     

A Novel Tantalum Cluster Chalcohalide Ta4S1.5Se7.5I8

Single crystals of Ta₄S_1.5Se_7.5I₈ are obtained by heating Ta, S, Se and I₂ at 300 °C in 4.0:1.0:8.0:4.4 molar ratio. The structure was determined by X-ray analysis and consists of molecular clusters [Ta₄(μ₄-S)(μ₂-Q_axSe_eq)₄I₈] (Q ≈ Se_0.87S_0.13). The tantalum atoms form a square with long Ta…Ta distances (3.26–3.32 Å), with four dichalcogenide ligands bridging the Ta–Ta edges and a sulfur atom capping the square. Each Ta atom has two terminal iodine atoms. Raman spectroscopy study shows the presence of the characteristic absorption band at 396 cm^?1 which is due to the Ta₄–μ₄-S vibrations. Cyclic voltammetry shows that Ta₄S_1.5Se_7.5I₈ in solid state undergoes quasi-reversible one-electron oxidation which is metal-centered.     

Synthesis and characterization of a novel tantalum chalcogen-rich molecular cluster with square planar metal core

Black single crystals of Ta(4)Se(9)I(8) are obtained in a high yield by heating Ta, Se, and I(2) at 300 degrees C in 1:2.2:1.0 molar ratio. In the structure, the tantalum atoms form a square, with four Se(2) ligands bridging the Ta-Ta edges and one capping the square. Each Ta atom has two terminal iodine atoms. The compound is diamagnetic and has only two electrons for metal-metal bonding.     

Synthesis and characterization of rhenium-copper sulfide cluster complexes [(Ph3P)2N][Re3(CuX)(mu3-S)4Cl6(PMe2Ph)3] (X = Cl, Br, I)

The reaction of a trinuclear rhenium sulfide cluster compound Re3S7Cl7 with dimethylphenylphosphine and CuX2 (X = Cl or Br) or CuX (X = Cl, Br, or I) formed tetranuclear cluster complexes [(Ph3P)2N][Re3(CuX)(mu3-S)4Cl6(PMe2Ph)3] (X = Cl, Br, or I). Their solutions have the characteristic intense blue color with visible spectral bands near 600 nm. Single-crystal X-ray structures show that three mu-S atoms in the intermediate trinuclear rhenium complex coordinate to a copper atom, forming elongated tetrahedral structures in which Re-Cu bonding interaction is negligible (Re-Cu distances are 3.50 to approximately 3.54 A as compared with Re-Re distances ranging from 2.69 to 2.81 A).     

Rearrangement of symmetrical dicubane clusters into topological analogues of the P cluster of nitrogenase: nature's choice?

Reaction schemes have been developed that lead to clusters having the topology of the PN cluster of nitrogenase. The single cubane clusters [(Tp)MFe3S4Cl3]z (M = Mo, z = 1-; M = V, z = 2-) react with PEt3 to give [(Tp)MFe3S4(PEt3)3]1+, which are reduced to the neutral edge-bridged double cubanes [(Tp)2M2Fe6S8(PEt3)4] with highly reduced (2[MFe3S4]1+) cores. Reaction of these clusters in acetonitrile with (Et4N)(HS) results in the formation of [(Tp)2Mo2Fe6S9(SH)2]3- and [(Tp)2V2Fe6S9(SH)2]4-. X-ray structures of the Et4N+ salts reveal the bridging pattern M2Fe6(mu2-S)2(mu3-S)6(mu6-S) in which two cuboidal MFe3(mu3-S)3 units share the common bridge atom mu6-S and are externally bridged by two mu2-S atoms. The M sites possess trigonal octahedral, and the Fe sites, distorted tetrahedral coordination. Hydrosulfide ligands and sulfide atoms simulate terminal cysteinate ligation and mu2 bridges, respectively, in the protein-bound cluster Fe8S7(mu2-SCys)2(SCys)4. The synthetic clusters have the same bridging pattern as the PN cluster and approach congruency with it. These clusters are the first molecular topological analogues of a PN cluster. Like the latter, they are substantially reduced (majority of Fe(II)).     

Cluster core controlled reactions of substitution of terminal bromide ligands by triphenylphosphine in octahedral rhenium chalcobromide complexes

Reactions of rhenium chalcobromides Cs4[{Re6(mu3-S)8}Br6].2H2O, Cs3[{Re6(mu3-Se)8}Br6].2H2O, Cs3[{Re6(mu3-Q)7(mu3-Br)}Br6].H2O (Q = S, Se), and K2[{Re6(mu3-S)6(mu3-Br)2}Br6] with molten triphenylphosphine (PPh3) have resulted in a family of novel molecular hybrid inorganic-organic cluster compounds. Six octahedral rhenium cluster complexes containing PPh3 ligands with general formula [{Re6(mu3-Q)8-n(mu3-Br)n}(PPh3)4-nBrn+2] (Q = S, n = 0, 1, 2; Q = Se, n = 0, 1) have been synthesized and characterized by X-ray single-crystal diffraction and elemental analyses, 31P{1H} NMR, luminescent measurements, and quantum-chemical calculations. It was found that the number of terminal PPh3 ligands in the complexes is controlled by the composition and consequently by the charge of the cluster core {Re6Q8-nBrn}n+2. In crystal structures of the complexes with mixed chalcogen/bromine ligands in the cluster core all positions of a cube [Q8-nBrn] are ordered and occupied exclusively by Q or Br atoms. Luminescence characteristics of the compounds trans-[{Re6Q8}(PPh3)4Br2] and fac-[{Re6Se7Br}(PPh3)3Br3] (Q = S, Se) have been investigated in CH2Cl2 solution and the broad emission spectra in the range of 600-850 nm were observed.     

Volatile imido-hydrazido compounds of the refractory metals niobium, tantalum, molybdenum, and tungsten

Volatile 1,1-dimethyl-2-(trimethylsilyl)hydrazido(1-) complexes of niobium, tantalum, molybdenum, and tungsten have been synthesized and fully characterized for use as precursors in their chemical vapor deposition to metal nitrides. Different reaction patterns were observed in the hydrazinolysis of imido complexes of those four metals with (trimethylsilyl)dimethylhydrazine HN(SiMe3)NMe2 (H-TDMH). [Ta(NtBu)Cl3Py2] gave [Ta(TDMH)2Cl3] (1) with loss of the imido functionality, and [M(NtBu)2Cl2Py2] gave [M(NtBu)2(TDMH)Cl] (M = W, 8a; Mo, 8b). Reactions of both types of metal imido complexes with magnesium hydrazides produced [M(NtBu)(TDMH)2X] (M = Ta, X = Cl, 2a; X = Br, 3a; M = Nb, X = Cl, 2b; X = Br, 3b) and [M(NtBu)2(TDMH)X] (M = W, X = Cl, 8a; X = Br, 9a; M = Mo, X = Cl, 8b; X = Br, 9b). Halogen substitution reactions at 2 and 3 by -NMe2, -NHtBu, and CH2Ph groups as well as imido ligand replacement reactions have been investigated. The results of crystal structure determinations of 1, 4a, 5a, 6a, 7b, and 9b are presented.     

异金属螺旋链化合物{[W_6Ag_6S_(24)][La(DMSO)_8]_2}_n的合成及结构表征

合成了异金属含硫化合物{[W6Ag6S24][La(Me2SO)8]2}n,并用X射线单晶衍射法测定了其结构.结果表明,该化合物属三斜晶系,P-墿空间群;晶胞参数为:a=1.577 5(3),b=1.818 7(4),c=1.952 3(4)nm,α=92.210(2)°,β=106.567(3)°,γ=92.494(2)°,Z=2,Dc=2.510 g/cm3,μ=9.081 mm-1,F(000)=3 792,R1=0.040 9,wR2=0.086 9.化合物中的阴离子[(W6Ag6S24)6-]n具有异金属螺旋链结构,所有W原子和Ag原子均与S原子形成四面体配位构型.     

Synthesis and Crystal Structur of (4,4''-H2bipy)[CdBr4]·H2O

The title compound (4,4'-H2bipy)[CdBr4]·H2O 1 has been synthesized via hydrothermal reaction and characterized by X-ray diffraction. The crystal belongs to monoelinic,space group P21/c with a=8.260(3), b=23.926(7), c=9.774(2) (A), β=106.777(9)°,C10H12Br4CdN2O, Mr=608.26, V=1849.4(9)(A)3, Z=4, Dc=2.185 g/cm3, S=1.005, μ(MoKα)=9.814 mm-1, F(000)=1128, R=0.0646 and wR=0.0989. The crystal structure analysis of 1reveals that the title compound features an isolated structure, based on discrete 4,4'-H2bipy moieties and lattice water molecules which are linked by hydrogen bonds together with tetrahedral cadmium atoms terminally coordinated by four bromine atoms.     

Synthesis and Crystal Structure of aNovelPolythiotungstate Compound[PPh4]2[（S）2W（μ—S）2（O）W（THF）（μ—S）2W（S）2]

1 INTRODUCTION Polythiotungstate complexes can be prepared from the protonation of one sulfur atom of [WS4]2－ and subsequent intramolecular redox reactions[1,2]. For example, [(S)2W(m-S)2W(m-S)2W(S)2]2 was formed by the acidification of a diluted aqueous solution of (NH4)2[WS4] with dilute H2SO4[3]. When a diluted aqueous solution containing [WS4]2 was acidified with 0.1mol/L HCl, [(S)2W(m-S)2(O)- W(H2O)(m-S)2W(S)2]2 was formed[4]. [(S)2W- (m-S)2(S)W(m-S)2W(S)2]2 was form…     

Synthesis and Structural Characterization of a Salt{[Co(Phen)3][Mo2S2(μ-S)2(edt)2]}2·(DMSO)2·(Et2O)(Phen = 1,10-Phenanthroline,edt = Ethane-1,2-dithiolate)

Reaction of [Et4N]2[Mo2S2(μ-S)2(edt)2] with CoCl2(6H2O and Phen in MeCN followed by recrystallization in DMSO/Et2O gave rise to dark-red block crystals of {[Co(Phen)3]- [Mo2S2(μ-S)2(edt)2]}2·(DMSO)2·(Et2O) 1 (C88H86Co2Mo4N12O3S18). 1 crystallizes in the monoclinic system, space group P21/c with a = 24.631(4), b = 16.117(3), c = 24.791(4) (A), β = 92.835°, V = 9829.3(3) (A)3, Z = 4, Mr = 2438.57, Dc = 1.648 g/cm3, F(000) = 4928, μ = 12.61 cm-1, R = 0.0936 and wR = 0.1682 for 12998 observed reflections with I > 2.0σ(I). In the structure of 1, the Co atom of the [Co(Phen)3]2+ dication is octahedrally coordinated by three Phen ligands. The Mo atom of the [Mo2S2(μ-S)2(edt)2]2- dianion is coordinated by two μ-S, one terminal S and two S atoms from edt, forming a distorted square pyramidal geometry. The mean Co-N and Mo…Mo bond distances are 2.139 and 2.872 (A), respectively.     

Synthesis and Crystal Structure of Trigadolinium Bromoorthosilicate，Gd_3Br（SiO_4）_2

ＳｙｎｔｈｅｓｉｓａｎｄＣｒｙｓｔａｌＳｔｒｕｃｔｕｒｅｏｆＴｒｉｇａｄｏｌｉｎｉｕｍＢｒｏｍｏｏｒｔｈｏｓｉｌｉｃａｔｅ，Ｇｄ_３Ｂｒ（ＳｉＯ_４）_２ＭａｏＪｉａｎｇ－Ｇａｏ；ＺｈｕａｎｇＨｏｎｇ－Ｈｕｉ；ＨｕａｎｇＪｉｎ－Ｓｈｕｎ（ＳｔａｔｅＫｅ?..     

Synthesis and Structural Characterization of a Salt {[Co(Phen)_3][Mo_2S_2(μ-S)_2(edt)_2]}_2·(DMSO)_2·(Et_2O)(Phen = 1,10-Phenanthroline,edt=Ethane-1,2-dithiolate)

1 INTRODUCTION Dinuclear sulfido-bridged complexes with M2S2(μ-S)2 unit serving as building blocks for the construction of mixed-metal clusters are well docu- mented due to their rich structure diversities[1～3] as well as their potential applications in catalytic sys- tems and eletro/photonic materials[4, 5]. For example, reaction of [CpEt2Mo2S2(μ-S)2] with 2 equiv. of Co- (CO)3(NO) gave rise to a cubane-like cluster com- pound [CpEt2Mo2S2(μ-S)2Co2(CO)2][6]. In the case of[Mo…     

Bonding trends of thiosemicarbazones in mononuclear and dinuclear copper(I) complexes: syntheses, structures, and theoretical aspects

Reactions of copper(I) halides with a series of thiosemicarbazone ligands (Htsc) in the presence of triphenylphosphine (Ph(3)P) in acetonitrile have yielded three types of complexes: (i) monomers, [CuX(eta1-S-Htsc)(Ph3P)2] [X, Htsc = I (1), Br (2), benzaldehyde thiosemicarbazone (Hbtsc); I (5), Br (6), Cl (7), pyridine-2-carbaldehyde thiosemicarbazone (Hpytsc)], (ii) halogen-bridged dimers, [Cu2(mu2-X)2(eta1-S-Htsc)2(Ph3P)2] [X, Htsc = Br (3), Hbtsc; I (8), furan-2-carbaldehyde thiosemicarbazone (Hftsc); I (11), thiophene-2-carbaldehyde thiosemicarbazone (Httsc)], and (iii) sulfur-bridged dimers, [Cu2X2(mu2-S-Htsc)2(Ph3P)2] [X, Htsc = Cl (4), Hbtsc; Br (9), Cl (10), pyrrole-2-carbaldehyde thiosemicarbazone (Hptsc); Br (12), Httsc]. All of these complexes have been characterized with the help of elemental analysis, IR, 1H, 13C, or 31P NMR spectroscopy, and X-ray crystallography (1-12). In all of the complexes, thiosemicarbazones are acting as neutral S-donor ligands in eta()S or mu2-S bonding modes. The Cu...Cu separations in the Cu(mu2-X)2Cu and Cu(mu2-S)2Cu cores lie in the ranges 2.981(1)-3.2247(6) and 2.813(1)-3.2329(8) Angstroms, respectively. The geometry around each Cu center in monomers and dimers may be treated as distorted tetrahedral. Ab initio density functional theory calculations on model monomeric and dimeric complexes of the simplest thiosemicarbazone [H2C=N-NH-C(S)-NH2, Htsc] have revealed that monomers and halogen-bridged dimers have similar stability and that sulfur-bridged dimers are stable only when halogen atoms are engaged in hydrogen bonding with the solvent of crystallization or H2O molecules.     

Synthesis and Crystal Structur of (4,4′-H_2bipy)[CdBr_4]·H_2O

The title compound (4,4′-H2bipy)[CdBr4]·H2O 1 has been synthesized via hydrothermal reaction and characterized by X-ray diffraction. The crystal belongs to monoclinic,space group P21/c with a=8.260(3),b=23.926(7),c=9.774(2),β=106.777(9)o,C10H12Br4CdN2O,Mr=608.26,V=1849.4(9)3,Z=4,Dc=2.185 g/cm3,S=1.005,μ(MoKα) =9.814 mm–1,F(000)=1128,R=0.0646 and wR=0.0989. The crystal structure analysis of 1 reveals that the title compound features an isolated structure,based on discrete 4,4′-H2bipy moieties and lattice water molecules which are linked by hydrogen bonds together with tetra-hedral cadmium atoms terminally coordinated by four bromine atoms.     

FeCo2(CO)7(μ3-S)(O[P(SCH2)2]2)的合成与晶体结构

许多化学工作者对单齿膦配体（ＰＰｈ３,ＰＢｕｎ３,ＰＥｔ２Ｐｈ,Ｐ（ＯＥｔ）３,Ｐ（ＯＣ６Ｈ５）３）与母体簇合物ＦｅＣｏ２（ＣＯ）９（μ３－Ｓ）的取代反应进行过详细研究［１－３］,但对双齿膦配体与母体簇合物的取代反应研究报导较少．Ａｉｍｅ［４］合成了含双齿膦配体的簇合物ＦｅＣｏ２（ＣＯ）７（μ３－Ｓ）（Ｐｈ２ＰＣＨ２ＰＰｈ２）,并用１３ＣＮＭＲ和ＩＲ光谱方法对其结构进行了表征．到目前为止,含双齿膦配体的该类簇合物的晶体与分子结构还未见报导．ＲｏｓａｎｎａＲｏｓｓｅｔｔｉ［２］通过研究母体簇合物与…     

CRYSTAL STRUCTURE OF TRINUCLEAR MOLYBDENUM CLUS-TER Mo_3(μ_3-S)(μ_2-S_2)_3(Et_2dtc)_3I SYNTHESIZED BY SOLID STATE REACTION

<正> The title cluster compound was synthesized by solid state reaction at low heating temperature. C15H30IMo3N3S13, Mr=1083. 93, monoclinic, P21/n, a = 14.396(3), b = 13. 116(3), c=18. 142(8)A;β= 91. 36(3)°; V =3425(2)A3, Z = 4. Dc = 2. 10g/cm3, F(000) = 2112,μ(MoKa) = 27. 29cm-1, final R = 0. 034, Rw = 0. 051 for 1845 unique observed reflections (I≥3σ(I)). The three Mo atoms form an equilateral triangle with an average side length of 2. 714 A. Each Mo atom is coordinated with seven S atoms forming a distorted pentagonal bipyramid. The iodine atom connects with three S atoms (out of the CMo3] plane) with an average distance of 3. 205 A.The title compound has similar cubane-like cluster core [Mo3S7I] as the compound Mo3(μ3-S)(μ2-S2)3(dtp)3I(dtp= (EtO)2PS2).     

Molybdenum-iron-sulfur clusters of nuclearities eight and sixteen, including a topological analogue of the P-cluster of nitrogenase

Transformations of the edge-bridged double cubane cluster [(Cl4cat)2(Et3P)2Mo2Fe6S8(PEt3)4] (1) under reducing conditions have been investigated as synthetic approaches to the clusters of nitrogenase. Cluster 1 is a versatile precursor to different Mo-Fe-S cluster types. The reaction system 1/K(C14H10) in THF yields the reduced cluster [(Cl4cat)2(Et3P)2Mo2Fe6S8(PEt3)4]1- (2), which as its crystalline Et4N+ salt retains the edge-bridged structure of 1. X-ray structural and M?ssbauer spectroscopic results indicate an unsymmetrical electron distribution with localized [MoFe3S4]2+,1+ cubane-type units. The system 1/2K(C14H10)/2HS- in THF/acetonitrile affords [(Cl4cat)4(Et3P)4Mo4Fe12S20K3(DMF)]5- (3), whose structure was determined as the Ph3PMe+ salt. The cluster consists of two isostructural Mo2Fe6S9 fragments connected by two mu 2-S bridges. Three potassium ions are bound between the two fragments. In each fragment, the iron atoms are present in tetrahedral FeS4 and the molybdenum atoms in octahedral MoO2PS3 coordination units, and two MoFe3(mu 3-S)3 cuboidal units are bridged by a common mu 6-S atom. The fragments have idealized mirror symmetry and are isostructural with two of the fragments present in the previously reported high-nuclearity cluster [(Cl4cat)6(Et3P)6Mo6Fe20S30]8- (4) (Osterloh, F.; Sanakis, Y.; Staples, R. J.; Münck, E.; Holm, R. H. Angew. Chem., Int. Ed. Engl. 1999, 38, 2066). On the basis of overall shape, atom connectivities, and metric features, the Mo2Fe6S9 fragment is a topological analogue of the P-cluster of nitrogenase in the PN (reduced) state. A third cluster type, formed as a minor byproduct in the reaction system leading to 2, was crystallographically identified as [(Cl4cat)2(Et3P)2Mo2Fe6S8(PEt3)4]4-, whose core is made up of two MoFe3(mu 3-S)3 cuboidal units bridged by two mu 2-S atoms and connected by a direct Fe-Fe bond. Full structural details and the redox properties of 2 and 3 are reported.     

Novel chelate ring-opening induced by silver(I) of five-coordinate palladium(II) and platinum(II) complexes containing tripodal polyphosphines

The ionic complexes [Pd(NP 3)X]X [NP 3 = tris[2-(diphenylphosphino)ethyl]amine, X = Cl (1), Br(2)] and [M(PP 3)X]X [PP 3 = tris[2-(diphenylphosphino)ethyl]phosphine, M = Pd, X = Cl (3), Br(4); M = Pt, X = Cl (5), Br (6)] contain square pyramidal (1, 2) and trigonal bipyramidal (3- 6) cations with three fused chelate rings to M and one M-X bond. By addition of AgX salts (X = Cl, Br, NO 3) an unexpected ring-opening reaction occurs with formation of the heteronuclear species PdAg(NP 3)X 3 [X = Cl (7), Br (8)], MAg(PP 3)X 3 [M = Pd, X = Cl (9), Br (10), NO 3 (13);M = Pt, X = Cl (11), Br (12), NO 3 (14)]. The complexes have been characterized in the solid state and solution. The X-ray crystal structures of 9 and 13 reveal a distorted square-planar arrangement to Pd(II) that is coordinated to three P of PP 3 (the central and two terminal atoms) and to one chloride (9) or one oxygen atom of NO 3 (13). The resultant dangling phosphorus of the ring opening is bound to Ag(I) that completes the three- [PAgCl 2 ( 9)] and four-coordination [PAg(ONO 2)(O 2NO) (13)] through the donor atoms of the anions with the nitrates in 13 unusually acting as both mono- and bidentate ligands. Complexes 7, 8, 10, and 11 undergo oligomerization in solution. Complex 10 oligomerizes giving rise to the ionic compound [Pd 4Ag 2(PP 3) 2 Br 9]Br ( 10a) whose X-ray crystal structure indicates the presence of cations with a Pd(mu-Br) 3Pd unit that connects via bromide bridges two BrPdP 2PPAg Br 2 fragments containing distorted square-planar and trigonal-planar Pd(II) and Ag(I) centers, respectively. The palladium(II) metal centers in the central unit afford the five-coordination (PdBr 5) with a distorted trigonal bipyramidal geometry. The ionic system [Pt 2Ag 2(PP 3) 2 Cl 5]Cl (11a) consists of chloride anions and heteronuclear monocations. The X-ray crystal structure reveals that the cations contain two distorted square-planar ClPtP 3 units bridged by one PAgCl(mu-Cl) 2AgP fragment that is bearing tetrahedral (PAgCl 3) and trigonal planar PAgCl 2 silver(I) centers. Further additions of the corresponding AgX salts to complexes 7- 14 did not give rise to any new ring-opening reaction.     

具有“松散”配体的两个三核钼簇合物的合成和晶体结构｛Mo_3(μ_3-S)(μ-S)_3[μ-S_2P(OC_2H_5)_2][S_2P(OC_2H_5)_2]_3(L)｝(L=C_5H_5N(Ⅰ),C_6H_5CH_2SH(Ⅱ))

报道了两个具有“松散”配体的三核相簇合物,的晶体和分子结构,其中晶体（Ⅰ）属于单斜晶系,空间群晶体（Ⅱ）亦属于单科晶系,Mr空间群结果表明,这两个分别通过松散配体取代法和简单Mo化合物的“自兜”反应法得到的产物均属于具有松散配体的三核相簇合物。簇分子均由Mo3和μ3－S构成[Mo3S],每两个Mo间又被一个μ-S所桥连。其中每个Mo周围进一步被一个μ-dtp中的S或一个松散配体（吮咬（Ⅰ）或卞硫醇分子（Ⅱ））以及端基dtp中的2个S所配位,从而使其形成具有六配位的八面体构型。