SYNTHESIS AND SPECTRAL STUDIES OF(μ-PHENYLTHIO) (μ-ALKYLTHIO) HEXACARBONYLDIIRON COMPLEXES

Through reductive reaction between PhL1 and μ-S2 Fe (CO/6,tollowed by nucleophilicsubstitution of the intermediate (μ-PhS} (μ-LIS} Fe2 (CO)6 toward RX,nine Fe-S clus-ter complexes of (μ-PhS)(μ-RS)Fe2(CO)6 series have been synthesized.The influence of RX structures on the activities in nucleophilic substitution has been examined and possible steroisomers and isomer ratios of the complexes determined.In addition,the regular variations of isomer's CH3-S and CH2-S which are caused by the anisotropic effects of C-O and orientations of unshared electron pairs on sulfurs,have also been preliminarily discussed.     

Ligand substitution reaction of (μ-H)Os3(CO)10(μ-COMe) with 1,1'-bis(diphenylphosphino) ferrocene

Reaction of (μ-H)Os₃(CO)₁₀(μ-COMe) with 1,1'-bis(diphenylphosphino)-ferrocene (dppf) produces (μ-H)Os₃(CO)₈(μ-COMe){μ-η²-(η⁵-C₅H₄PPh₂)₂Fe} (1) and (μ-H)₂Os₃(CO)₇(μ-COMe){μ-η³-(η⁵-C₅H₃PPh₂)Fe(η⁵-C₅H₄PPh₂)} (2). Thermolysis of 1 leads quantitatively to 2. These compounds have been characterized by ¹H, ³¹P, and ¹³C NMR, IR, and mass spectroscopies. Compound 2 crystallizes in space group P 2₁/c with a = 11.898(2), b = 21.266(3), c = 18.262(3) Å, β = 104.71(1)°, V = 4469(1) ų, Z = 4, and R_F = 0.029.     

Synthesis and characterisation of hexanuclear ruthenium clusters containing a μ4-nitrene ligand. Crystal structures of [Ru6(CO)15(μ-CO)2(μ4NH)(μ-OMe)μ3-η2-N(H)C(O)OMe] and [Ru6(CO)16(μ-CO)2(μ4-NH)(μ-OMe)(μ-NCO)]

Two hexaruthenium carbonyl clusters [Ru₆(CO)₁₅(μ-CO)₂(μ₄-NH) (μ-OMe){μ₃-η²-N(H)C(O)OMe}] and [Ru₆(CO)₁₆(μ-CO)₂-(μ₄-NH)(μ-OMe)(μ-NCO)]2 have been isolated from the pyrolysis of H₂Ru₃(CO))₉NOCH₃, and single-crystal X-ray structure analysis shows that both 1 and 2 have a square planar arrangement of four ruthenium atoms capped by a μ₄-nitrene ligand, with two additional ruthenium atoms bridging two opposite RuRu edges of the square base to form a ‘boat’ form metal framework.     

(μ-RS)(μ-XMgS)Fe2(CO)6亲核性能的研究:铁硫配合物(μ-RS)[μ-Cp(CO)2FeS]Fe2(CO)6

研究了(μ-RS)(μ-XMgS)Fe2(CO)6与π-环戊二烯二羰基碘化铁的反应.首次制得(μ-RS)[(μ-CpFe(CO)2S]Fe2(CO)6的一系列含有机铁硫桥的非对称配合物.它们的核磁氢谱表明每个络合物只是以一类构象体存在.它们的甲基络合物的单晶结构分析证实了这一结论.     

双簇核铁硫配合物[(μ-RS)Fe2(CO)6]2(μ-S-S-μ)的合成

本文报导由μ-S2F2(CO)6及格氏试剂形成的活泼配合物(1), 可在磺酰氯SO2Cl2的作用下, 发生氧化偶联反应生成由S-S键相连的双簇核配合物(2), 本文对所得配合物(2)的反应性能进行了研究。     

Rh2(CO)4(μ-Cl)2和Rh4(μ-CO)3(CO)4的简正振动分析

金属簇合物具有独特的结构和成键方式。本文对铑簇合物的简正振动分析进行了研究。通过红外光谱用石蜡油糊涂KBr和聚乙烯窗口, 在Nicolet 200SXV FT-IR光谱上测定了Rh2(CO)4(μ-Cl)2的构型, 并使用分子振动全分析程序MVTA(Basic语言), 在PC机上进行计算。     

THE SYNTHESIS AND CRYSTAL STRUCTURE OF Mo_3(μ_3-O)-(μ-S)_3(μ-OOCCH_3)(dtp)_3(Py)

<正> The title compound was obtained by the reaction of Mo3(μ3-O) (μ-S)3(dtp)4(H2O) with CH3COONa and pyridine. Mo3C19H38N1O9P3S9,Mr= 1093. 79, triclinic, space group P1, a = 12. 921(3) , b = 14. 260(3) , c= 12. 800(3)(?),α = 97. 54(2), β=116. 66(1), γ=100. 10(2) °, V = 2015, 2(8)(?)3, Z=2, Dc = 1. 80gcm-3, F(000) = 1092, final R = 0. 066 for 3444 observations, room temp. In the structure the three Mo atoms form an isosceles triangle capped by a μ3-O atom with three sides of 2. 589(2) , 2. 642(2), and 2. 627(2) (?) respectively, and the car-boxyl bridged Mo-Mo bond is the shortest one.     

Synthesis and Structure of a Novel Mg6 Cluster Molecule Mg6(μ3-OH)2(μ3-Br)2(μ-Br)8(THF)8

A novel Mg₆ cluster molecule with the formula of Mg₆( ₃-OH)₂( ₃-Br)₂(-Br)₈(THF)₈ (1) has been isolated in 38% yield from a reaction of the Grignard reagent, 2-naphthyl-Mg-Br with BBr₃ in THF. The structure of 1, determined by a single-crystal X-ray diffraction analysis, contains two Mg₃ triangles linked together by two bridging bromide ligands. Within each Mg₃ triangle, one hydroxide and one bromide ligand function as triply bridging ligands capping both sides of the Mg₃ triangle. The coordination geometry around each Mg(II) ion is approximately octahedral. NMR studies revealed that compound 1 is highly fluxional in solution.     

Co_3(CO)_9(μ_3-PR)、Co_4(μ-CO)_2(CO)_8(μ_4-PR)_2和Co_2Fe(CO)_9(μ_3-PR)原子簇化合物合成与结构

本文合成了数个以有机磷作桥基配位体的同核钴和异核铁钴原子簇羰基化合物.通过元素分析、IR谱和~1H-NMR谱测定,确定三核钴簇合物Co_5(CO)_9-(μ_3-PR)和异核铁钴簇合物Co_2Fe(CO)_9(μ_3-PR)的分子骨架Co_3P和Co_2FeP具有三角锥构型,而四核钴簇合物Co_4(μ-CO)_2(CO)_8(μ_4-PR)_2的分子骨架Co_4P_2为八面体构型.     

μ-phenoxo-bridged binuclear copper(II) complexes

Summary Two -phenoxo-bridged binuclear copper(II) complexes, [Fsal(GG)₂Cu₂Cl₃]·H₂O (1) containing an exogenous chloride-bridge and [Fsal(GG)₂Cu₂(OH)](ClO₄)₂·H₂O (2) containing an exogenous hydroxide-bridge, where {Fsal(GG)₂ = 2,6-bis[N-(acetylglycine)-imino-methylene]-4-methylphenol}, were synthesized. The complexes were characterized be several spectroscopic methods. According to variable temperature magnetic susceptibility measurements (4–300 K), the hydroxide-bridged complex (2) has a weak antiferromagnetic spin exchange integral (J =- 23.6 cm), while the chloride complex (1) has an unusual weak ferromagnetic spin exchange integral (J = + 30.9 cm); both complexes have similar optical spectra in the aqueous solutions.     

CRYSTAL STRUCTURE AND REACTIVITY OF (Et_4N) [Mo_3(μ_6-O)-(μ-Cl)_3(μ-OAc)_3Cl_3]

<正> (Et4N)[Mo3(μ3-O)(μ-Cl)3(μ-OAc)3Cl3], C14H29Cl6Mo3NO7, Mr = 823.92, triclinic, P1, a = 17. 508(4), b = 19. 602(3), c=8. 091(2)A, α=91. 25(2)°, β= 96. 56(2)°,γ= 83. 61(2)°, V = 2741(1)A3, Z = 4, Dc = 2.00g/cm3, MoKa (λ=0. 71069A), μ= 19. 44cm-1, F(000) = 1616, T = 23℃, final R = 0. 055, Rw = 0. 068 for 5728 unique intensity data (I≥3σ(I)).The molecule consists of cluster aniorn [Mo3(μ3-O) (μ-Cl)3(μ-OAc)3Cl3]- and cation (Et4N) + . There are two independent molecules in an asymmetric unit whose cluster anions A and B have the same configuration except for some bonding parameters. The cluster core may be described as an equilateral {Mo3} triangle with a capping O atom and three bridging Cl atoms below and above it respectively. In addition, each pair of Mo atoms is bridged by an acetate group and each Mo atom is further coordinated to a terminal chlorine atom. The three Mo - Mo bonds are 2. 587 (2), 2.587(2), 2. 582(2) A for cluster anion A and 2. 587(2), 2.595(2), 2.577 (2) A for cluster a     

CRYSTAL STRUCTURE OF (Et_4N)2 [Mo_3 (μ_3-O) (μ_3-Cl) (μ-Cl)_3 Cl_6]·EtOH

<正> Mr=963.9, monoclinic, P21/c, a=11.379(3), b=20.766(2), c=14.487(3) A,β=91.49(2)°, V=3518.9A3, Z=4, Dm=1.81, Dx=1.819 g·cm-3, MoKα radiation, λ=0.71073A, μ=18.167, F(000)=1916, T=293 K, R=0.040 for 3261 reflections. The structure consists of two sets of tetraethylammonium cations and trinuclear Mo cluster anions. The cluster skeleton is formed by three Mo atoms arranged in an isosceles triangle with a Cl and an O atoms as capping ligands.     

双簇核铁硫配合物[(μ-RS)Fe_2(CO)_6]_2(μ-S-S-μ)的合成

双簇核铁硫配合物的研究已引起人们的兴趣,据文献报道,由μ-S_2Fe_2(CO)_6及格氏试剂形成的活泼配合物(1)可在磺酰氯SO_2Cl_2的作用下发生氧化偶联反应,生成由     

Poly­[copper(II)-μ-pyrazine-μ3-squarato]

In the structure of the title compound, [Cu(C₄O₄)(C₄H₄N₂)]_n, each copper cation is surrounded by three squarate (3,4-di­hydroxy-3-cyclo­butene-1,2-dioate) anions and two pyrazine ligands, all of which are located in special positions. The copper cation and all atoms of the squarate anion are located on a mirror plane, whereas the pyrazine ligand is located around a mirror plane which is perpendicular to the ring plane. The cations are connected via the squarate anions and the pyrazine ligands, forming sheets parallel to (001).     

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.     

Cp*MCpMoFe(CO)7(μ3-S), Cp*MoCpMFe(CO)7(μ3-S) (M = W,Mo) and Cp*WCp*MoFe(CO)7(μ3-S). Crystal structure of CpMoCp*WFe(CO)7(μ3-S)

CpMoFeCo(CO)₇(₃-S) reacts with Cp^*M(CO)₃Cl or CpM(CO)₃Cl (M=W, Mo) to gave the mixed-metal clusters Cp^*WCpMoFe(CO)₇(₃-S) (1), Cp^*MoCpMoFe(CO)₇(₃-S) (2), CpWCp^*MoFe(CO)₇(₃-S) (3), CpMoCp^*MoFe(CO)₇(₃-S) (4) and Cp^*WCp^*MoFe(CO)₇(₃-S) (5). The title clusters have been characterized by i.r., ¹H/¹³C-n.m.r. spectroscopy and their compositions have been confirmed by elemental analyses. The X-ray crystal structure analysis shows the two independent enantiomeric molecules of clusters (1) in one crystal structure unit.     

CRYSTAL AND MOLECULAR STRUCTURE OF (μ-SPh) (μ-SCH2CH2CN)Fe_2 (CO)_6

<正> The crystal and molecular structure of (μ-SPh)(μ-SCH2CH2CN)Fe2-(CO)5 has been determined by X-ray diffraction method. The crystals of this complex are triclinic, space group P1,with a=ll.175(1), b=ll.877(2), c= 15.640(2)1,α=106.20(1),β=103.15(1),γ=98.46(1)°; Z=4; Dc=1.67g/cm3. The final structure refinement converged with unweighted and weighted R factors of 0.028 and 0.034 for 2853 observed unique reflections.     

Bis{(μ-acetato)[μ-bis(salicylidene)-1,3-propanediaminato]zinc(II)}zinc(II)

In the title linear trinuclear compound, [Zn{Zn(CH₃COO)(C₁₇H₁₆N₂O₂)}₂], the central Zn²⁺ ion, which is located on an inversion centre, has a distorted octahedral coordination involving four bridging O atoms from two N,N′-bis­(salicyl­idene)-1,3-propane­diaminate ligands in the equatorial plane and one O atom from each bridging acetate group in the axial positions. The coordination around the terminal Zn²⁺ ion is irregular square pyramidal, with two O and two N atoms of the ligand in the basal plane and one O atom from an acetate group in the apical position. The acetate bridges linking the central and terminal Zn²⁺ ions are mutually trans. The Zn⃛Zn distance is 3.0520 (8) Å. The relationship of this structure to that of [Zn{Cu(CH₃COO)(C₁₇H₁₆N₂O₂)}₂] is discussed.     

Chemical Synthesis Studies on Pb Zr Alkoxides: A New Pb-Zr Structural Type,Pb3Zr7(μ4-O)4 (μ3-O)4(μ-O2CCH3) 8(μ-OiPr)6(Oi Pr)4

The compound [Pb₃Zr₇(₄-O)₄ (₃-O)₄(O₂CCH₃)₈ (OPrⁱ)₁₀] has been isolated from a reaction mixture containing known Pb-Zr and Pb-Ti complexes and characterised by ²⁰⁷Pb and ¹ H NMR and IR spectroscopy. The compound crystallises in the space group P with a = 13.778(4) Å, b = 21.916(5) Å, c = 27.768(10) Å; = 86.52(3)°, = 87.68(3)°, = 72.72(2)° V 7989(4) ų, Z = 4, R = 0.0973. A Pb-Zr alkoxide complex containing acetylacetone has also been synthesised using PbO as a reagent having the composition [Pb₂Zr₄(O)₂ (OⁱPr)₆(OⁿPr)₈ (acac)₂] allocated on the basis of MW, mass spectral and ¹H NMR data.