SYNTHESIS AND STRUTURE OF THE FIRST INTERSTITIAL μ_7-S CLUSTER Co_7(μ_7-S)(μ_4-PSEt)(μ-SEt)_2(μ-CO)_2(CO)_(12)

The reaction of Co_2(CO)_8 with EtSPCl_2 gives a new crystal like compound Co_7(μ_7-S)(μ_4-PSEt)(μ-SEt)_2(μ-CO)_2(CO)_(12),whose structure has been determined by single crystal x-ray diffraction.This special com-pound reveals some new features in cluster chemistry~1:The fragmentation of a ligand precursor EtSPCl_2 yieldsthree kinds of fragments,μ_7-S,μ_4-PSEt and μ-SEt,which are ligands in the same cluster molecule.There is anew type of bridging S presented——A μ_7-S atom is interspaced into seven Co core.     

Synthesis, Structure and Properties of (n-Bu_4N)_3[Mo_6O_18NNAr(NO_2)_2]

The title compound was synthesized and characterized by means of elemental analysis, IR, DTA-TG and UV. Its single crystal structure was solved by using direct methods. The compound crystallizes in the orthorhombic space group Pmc(?) with lattice parameters: a = 1. 7261(2), b=l. 7537(3), c=2. 4258(3) nm. V=7. 34220 nm3, F(000) = 3648, Z = 4. The structure was refined to conventional discrepancy factors of R=0. 060 for 3176 observed reflections [Ⅰ>3σ/(Ⅰ)]. The anion represents a modification of the well-known [Mo6O19]2- anion, in which a single terminal oxo group is replaced by a 2,4-dinitrophenyl hydrazine ligand while the structure integrity of the hexanuclear framework is maintained.     

CRYSTAL AND MOLECULAR STRUCTURE OF TRIS(TRIPHENYLPHOSPHINE) TRI-CARBONYL-BRIDGED TRIPLATINUM CLUSTER COMPOUND Pt_3(μ2-CO)_3(Ph_3P)_3

<正> PRELIMINARY INFORMATION. The title compound, is one of the products synthesized by a reaction of bis(triphenylphosphine)-platinum, carbon monoxide and chlorine gas in sodium hydrate solution at room temperature. An X-ray structural analysis has been undertaken to clarify unambiguously the arrangement of ligands around the triangle platinum cluster core. This has been     

Synthesis and crystal structure of a novel two-dimensional network complex [Mn(O_2CCH_2Cl)_2(phen)]_n

A novel two-dimensional network manganese(Ⅱ) polymer complex [Mn(O2CCH2CI)2-(phen)]n has been synthesized and characterized by elemental analysis and IR spectrum. The crystal structure of title complex has also been determined, which is in monoclinic of a space group P21/c with the following unit cell parameters at 294K: a =1.9738(4) nm, b =1.1384(2) nm, c =0.74915(14) nm, V=1.6795(5) nm3, Z= 2.     

THE SYNTHESIS AND CRYSTAL STRUCTURE OF A NOVEL TETRANUCLEAR COPPER (Ⅰ) CLUSTER COMPLEX, Cu_4(α-C_(10)H_7CSS_2)_4·1/2CS_2

The title compound has been synthesized by the reaction of sodium α-dithionaphthoatewith CuCl_2 in an alkaline aqueous solution or by the reaction of α-dithionaphthoic acid withCuCl_2 in an organic solvent, The crude product was recrystallized in a mixture of CS_2 andC_2H_5OH. The crystals obtained are red and stable in air. The structure of the title compound is determined by a single-crystal X-ray diffractionanalysis. The crystal belongs to monoclinic space group C_(2h)~5- P(2_1/a) with unit cell parameters:a= 16.453(3)A, b=12.651(4)A, c=23.182(7)A, β=100.5(2)°, V=4744.6A~3,Z=4. Thestructure was refined to R=0.06 for 4707 reflections. In the molecule, Cu_4 cluster has a distorted tetrahedral configuration. Surrounding thistetrahydron are four α-perthionaphthoate ligands, coordinated to copper through the sulfuratoms. One of the sulfur atoms in each ligand forms sulfur bridge with copper atoms,while the other is coordinated to only one copper. The three Cu--S bonds formed by thethree sulfur atoms with a given copper atom are approximately coplanar. Each group--C--S_2 with Cu atom on a vertex of the tetetrahedron forms a five-member ring. Thesefive-member rings are also approximately cooplanar. The molecule possesses an approachingS_4 point symmetry. The mechanism for the formation of the title compound involves a redox reaction.which is discussed in this paper.     

A new route to prepare the mixed oxo-ethylidynecapped trinuclear tungsten(Ⅳ)cluster and the crystal structure of H_2Na_3[W_3O(CCH_3)(O_2CCH_3)_6(H_2O)_3][H_2W_(12)O_(40)]·13.5H_2O

The synthesis and the structural characterization of the title compound H_2Na_3[W_3O(CCH_3)-(O_2CCH_3)_6(H_2O)_3][H_2W_(12)O_(40)]·13.5 H_2O are described.It is known that the mixed oxo-ethylidyne-capped tritungsten cluster can be obtained by Zn dust reduction of Na_2WO_4·2H_2O in acetic anhydride.The title compound has been characterized by X-ray diffraction,UV/VIS and ~1H NMR spectra.The tungsten atoms in the cluster cation and anion are in the oxidation states of W(IV)and W(VI)respectively.The crystal is rhombohedral with the space group R32,a=17.058(3),c=49.665(9),γ=120°,V=12516(9)~3,Z=6,final R=0.037 for 2071 reflections with I≥3σ(I).Boththe cluster cation and anion have a C_3 symmetry.The important interatomic distances in angstroms forthe cluster cation are:W—W,2.730(2);W—μ_3-O,2.00;W—O(carboxyl),2.12;W—O_t,2.18(2).     

THE SYNTHESIS AND CRYSTAL STRUCTURE OF A NOVEL MOLYBDENUM-COPPER-SULFUR CLUSTER COMPOUND [(CH_3CH_2 )_4N]_2 [(μs-S)CusS_6(S_2)_6Mo_6O_6].DMF

The synthesis and crystal structure of a novel molybdenum-copper cluster compound with [(μs-S)Cus] core is reported. It was prepared from Cu2Br2 upon reaction with molybdenum sulfur compound [CH3CH2)4N]2[Mo2O2S2-(S2)(S4)]. The title compound crystallizes in the monoclinic system space group Cc with cell dimensions: a=21.320(5), b=21.869(3), c=13.029(5)A,β=118.28(1)°,Z=4, V=5349A3 and Dc=2.48 g.m-3. The structure has been determined by Patterson and Fourier methods and then refined by the least squares method to a final R of 0.053. There are some distortions from octahedron in configuration of the [(μs-S)Cu6]6 core with three weak Cu-Cu bonds.     

A Novel Way to Prepareγ-A1_2O_3 Supported SO_4~(2-)/ZrO_2 Solid Superacid Catalysts for n-Butane Isomerization

The isomerization of n-butane to isobutane, which is a valuable precursor for theproduction of MTBE and alkylated gasoline, on strong acid catalysts is an importantprocess in refining industry. Solid superacid, especially sulfated zirconia, has highcatalytic activity in n-butane isomerization at comparatively low temperatures andtherefore has attracted more attention of researchers in the past twenty years.' However,from the view point of practice, the activity of SZ needs to be improved fur…     

THE CRYSTAL STRUCTURE OF Mo_203[S_2P(OC_2H_5)_2]_4

<正> Introduction. In an attempt to synthesize Mo cluster compounds from the high-valenced Mo compounds in P_2S_5/EtOH-HC1 system we have obtained a brownblack rhombohedral crystal. The composition of it Mo_2O_3[S_2P(OC_2H_5)_2]_4 has been confirmed by X-ray single crystal structure determination, which reveals that the crystal structure is different from that by Knox, J. R. & Prout, C. K. (1969).     

RESEARCH ON TRINUCLEAR MOLYBDENUM CLUSTER COMPOUNDS——CRYSTAL AND MOLECULAR STRUCTURE OF Mo_3(μ_3-S)(μ_2-S_2)_3[S_2P(OEt)_2]_3Cl

The title crystal is straw-yellow in colour, belonging to the triclinic system. The space group is P with the following unit cell parameters:a=11.570(2), b=13.093(1), c=14.399(2), α=102.62(1), β=102.15(1), γ=111.87 (1)°, V=1870(1), Z=2, D_(calc)=1.960g·cm~(-3).The crystal structure was solved by the heavy atom method and refined by full-matrix least-squares to a final conventional R factor of 0.055. The results show that the crystal structure consists of neutral trinuclear Mo cluster molecules, in which three independent Mo atoms form an equilateral triangle with an average side length of 2.725(3), corresponding to a Me-Me single bond. On one side of the triangle one μ_3-S atom binds the three Mo atoms together to form a monoeapped trinuclear cluster. In addition, three S_2 radicals acting as μ_2 bridges are located between each two Mo atoms. Each Mo atom is also coordinated to two terminal S atoms of an [S_2P(OEt)_2]~- radical so as to complete a distorted pentagonal bipyramid configuration.     

RESEARCH ON TRINUCLEAR MOLYBDENUM CLUSTER COMPOUNDS——CRYSTAL AND MOLECULAR STRUCTURES OF (Et_4N)_2[Mo_3(μ_3-O)(μ_2-Cl)_3(Oac)_2Cl_5]

The title compound forms black crystals shaped like pseudo-octahedrons, which belong to the orthorhombic system The space group is Pna 2_1 with unit cell parametrs of a=17.815(1), b=16.629(2), c=12.003(1), and with Z=4, D_(obs)=1.80g·cm~(-3), and D_(calc)=1.804g·cm~(-3). The crystal structure was solved by the heavy atom method and refiened by fullmatrix least-squares to a final conventional R factor of 0.048 for 2584 unique reflections with I≥σ(Ⅰ). The investigation confirms that the crystal structure consists of tetraethylammonium cations and trinuclear Mo cluster anions. The anion is a μ_3-O monocapped trinuclear cluster with an average Mo-Mo bond length of 2.60 (2). On the side of the Mo_3 triangular plane opposite to the μ_3-O atom, each two Mo atoms are bridged by a Cl atom with the result that these seven atoms (3 Me, 1 O and 3 Cl atoms)form an apex-deficient quasicubane configuration. In addition, each Mo atom is coordinated to three additional atoms resulting in a pseudo-octahedral geome     

Synthesis,Structure and Properties of a New Terbium(Ⅲ) Complex Tb_2(C_(15)H_(11)O_3)_6(phen)_2

A new terbium(Ⅲ) complex Tb_2(C_(15)H_(11)O_3)_6(phen)_2 has been synthesized with 2-(4-methylbenzoyl)benzoic acid and 1,10-phenanthroline as ligands.Crystal data for the complex are as follows:monoclinic,space group P2_1/n,a=15.0786(6),b=13.5762(5),c=22.9683(9) A,β=104.130(4)°,V=4559.6(3) A~3,D_c=1.540_g/cm~3,Z=2,μ(MoKα)=1.615 mm~(-1),F(000)=2136,the final R=0.0528 and wR=0.0740.The Tb(Ⅲ) ion is coordinated by eight atoms to give a distorted square antiprism coordination geometry.The complex shows four fluorescence emission bands arising from the transitions of Tb~(3+5)D_4→~7F_6(490 nm),~5D_4→~7F_5(546 nm),~5D_4→~7F_4(588 nm) and ~5D_4→~7F_3(622 nm).The complex is an antiferromagnet in the range of 300～2 K.Also reported in the paper is the thermal stability property of the title complex.     

A novel one-dimensional organic-inorganic polymer: synthesis and crystal structure of[{Ca(DMF)_5}_2SiMo_(12)O_(40)]_n

A novel polyoxometalate-based organic-inorganic polymer [{Ca(DMF)5}2SiMo12O40]n has been synthesized and characterized by elemental analysis, IR, UV and X-ray single-crystal structural analysis. The title compound crystallizes in a monocline lattice, P21/n, with a =1.3379(3), b = 1.9796(4), c = 1.4574(3) nm, β = 92.24(3)°, V = 3.8568(13) nm3, Z = 2, R1 = 0.083 and Rw = 0.2065. The result of crystal structure analysis indicates that Ca2+ is surrounded by seven coordination oxygen atoms with pentagonal bipyramidal geometry and bridged with terminal oxygen atom of polyanion in the structure. The compound contains an unprecedented one-dimensional linear chain built by alternate polyanions and cationic units through Mo-Od-Ca-O-Ca links in crystal. The IR spectra and X-ray crystallography analysis exhibit that there is a strong interaction between the polyanion and organic group in solid state. The electronic spectra (λ = 200-500 nm) for the title compound dissolved in the mixed solvent of acetonitrile and     

(Et_4N)_2[Fe_4(SPh)_10] Stimulated S_(RN)1 Reactions of α-Bromonaphth-alene with Pinacolone Carbanion

The studies of the radical chain nucleophilic substitution reaction (SRN1) have been active field in both mechanism and organic synthesis research1-4. The mechanism is a well known process by which a nucleophilic substitution is produced on a non-actived adequated substituted substrate. It is a chain process which involves radicals and radical anions as intermediates. The main steps of this mechanism are sketched in scheme 1. As stimulated methods of initiation step, the photostimulated5-7, …     

Ship-in-bottle formation of Ru_3(CO)_(12) in NaY zeolite

NaY zeolite entrapped Ru3(CO)12 cluster has been synthesized from RuCl3 ion-exchanged NaY, which is well characterized by IR and Raman spectroscopies and CO chemisorp-tion. When the Ru3+/NaY sample is heated from 298 K to 393 K for 25 h and for 10 h at 393 K, the sample colour changes from dark to brown-yellow. The in situ infrared spectrum exhibits absorption bands at 2130, 2064, 2040, 2017, 1990, 1953 and 1925 cm-1. The bands at 2130 cm-1 arises from the Runm+(CO)l m =1-3;n = 1 - 3; l = 1-12). The bands at 2064, 2040, 2017 and 1990 cm-1 are proposed to be associated with the Ru3(CO)12/NaY, which are close to Ru3(CO)12 crystalline. Furthermore, the Raman results provide bands at 150 and 185 cm-1, which can be attributed to Ru-Ru bonds of the sample as in the case of Ru3(CO)12 crystalline, for which the A1' Ru-Ru stretching mode is assigned to 185 cm-1 and E1' Ru-Ru stretching mode is assigned to a band at 150 cm-1, respectively. CO chemisorption of [Ru3]/NaY gives a CO/Ru ratio of 3.85, which is simila     

[Na_4(H_2O)_7][Fe(OH)_6Mo_6O_(18)]: a new [12] metallacrown-6 structure with an octahedrally coordinated iron at the center

The reaction of an aqueous solution of sodium molybdate with iron powder at low pH (-0.184) gives rise to the formation of a six-member Mo ring-shape cluster with an Fe (II) encapsulated at the center, [Na4(H2O)7][Fe(OH)6Mo6O18](1), which is further linked to a remarkable three-dimensional network via sodium ions.     

SYNTHESIS AND STRUCTURE OF TETRANUCLEAR MOLYBDENUM CLUSTER COMPOUND[Mo_4S_4(μ-O_2CC_6H_5)_2(dtp)_4]

The cluster compound[Mo_4S_4(μ-O_2CC_5H_5)_2(dtp)_4](dtp=S_2P(OEt)_2)wasobtained by the ligand substitution reaction of tetranuclear molybdenum cluster[Mo_4S_4(μ-dtp)_2(dtp)_4]in the mixed solvent of acetone,ethanol and water in thepresence of C_6H_5CO_2Na.It is monoclinic and crystallizes in space group C2/c,Mr=1495.09,a=12.175(5),b=22.01(1),c=20.875(9),β=99.04(4)°;V=5575(5);Z=4;Dc=1.78g/cm~3.Final R factor is 0.066.The result reveals that the[Mo_4S_4]clustercore and t-(dtp)~(-1)ligands are retained and only μ-bridged(dtp)~(-1)ligands aresubstituted by(C_6H_5CO_2)~(-1)in the substitution reaction,thus producing the newtitle cluster compound,the structure of which contains two species of bidentateligand.     

Synthesis, Crystal Structure and Magnetic Property of Sanwich-Type Heteropolyoxometalate Na_9[{Na(H_2O)_2}_3{Cu(H_2O)}_3(BiW_9O_(33))_2]·42H_2O

Introduction The chemistry of the sandwich-type heteropoly-oxometalates encapsulating clusters of early transition metals is current of considerable interest with respect to the application of complexes in material science, medi-cine, catalysis and fundamental perspectives.1-4 The great advantage of these complexes is the possibility of varying either the type of the metallic cluster or the het-eroatom. The proximity of the transition metals pos-sessing unpaired electrons facilitates their cou…     

CRYSTAL AND MOLECULAR STRUCTURE OF {Fe_6Mo_2S_8(S-t-Bu)_6(OMe)_3}(Et_4N)_3

<正> Introduction. The title compound has been synthesized by reaction of {(SR)_2FeMoS_4}2-with {Fe_4(SR) 10}~2- (R=t-Bu) in methanol. It is interesting to note that the complex, which involves two {Fe_3MoS_4}cubane-like clusters, is generally regarded as the best model compound for molybdenum center of nitrogenase. The synthesis and property of {Fe_6Mo_2S_8(S-tBu)_6(OMe)_3}~3- have been discribed. Although it has previously been noted that the structure of this complex is similar to its tungsten analog, the detail structural report of the title compound has not yet been given.     

CRYSTAL STRUCTDBE OF H_2(Et_4N)_2[Mo_8O_(26)]

<正> Mr= 1446.02, Monoclinic, P21/n, a = 11.841(2),b= 20.008(6), c= 12.053(8)A,β=105.15(3)°,V= 2756(3)A3,Z= 2, DC = 1.738 g·cm-3. Final R=0.035 for 4326 reflections. The title compound is the decomposition product of the trinuclear Mo cluster anion [Mo3(μ3-O)(μ-Cl)3(μ-OAc)3Cl3]-. The [No8O26]4- anion reported here has the a -type configuration, which consists of a ring made up of six edge-sharing [MoO5] octahedra linked loosely to two [MoO4] units.