CRYSTAL STRUCTURE OF Mo_3(μ3-S)(μ-S)_3 (μ-C_2H_5COO)(dtp)_3Py

<正> C20H40Mo3NO8P3S10, Mr=1123.93, triclinic, P1,a=12.972(3), b=13.763(2), c= 14.515(7)A,α=66.22(3),β=101.72(3),γ=118.90(1)° , V= 2076(2) A3, Z=2,Dc=1.798 g.cm-3, MoKa radiation, final R= 0.040 and Rw=0.056 for 5645 observed reflections. The molecule contains three Mo atoms arranged in a triangle with one capping-S atom, three (μ-S) atoms, one (μ-EtCOO) ligand, one chelate ligand dtp on each Mo atom, and one terminal Py on atom Mo(1). The coordination of Mo atoms is of distorted octahedron.     

Crystal structure of [Pd3(μ-OH)(μ-CH3COO)5]

The crystals of the [Pd₃(μ-OH)(μ-CH₃COO)₅] complex are obtained and characterized using powder and single crystal X-ray diffraction and IR spectroscopy. The crystal structure (a = 15.6942(6) Å, b = 11.7190(3) Å, c = 9.7871(3) Å, V = 1800.05(10) ų, space group Pna2₁, Z = 4) is formed from neutral trinuclear cyclic molecules of [Pd₃(μ-OH)(μ-CH₃COO)₅], in which the OH^? group, together with five CH₃COO^? anions, is a bridge ligand.     

过渡金属μ3-E立方烷簇合物(η ^5-C5H5)4Fe4(μ3-Se)4及 (η ^5-RC5H4) 4Cr4(μ3-S)4的合成与表征

通过 (η5 C5H5) 2 Fe2 (CO) 4和硒粉在沸腾的甲苯中反应可制得含 μ3 Se的立方烷簇合物 (η5 C5H5) 4Fe4 (μ3 Se) 4(1) ,而由 (η5 RC5H4 ) 2 Cr2 (CO) 4S在甲苯中回流可制得含 μ3 S的立方烷簇合物 (η5 RC5H4 ) 4Cr4 (μ3 S) 4(2 ,R =COMe ;3,R =CO2 Me)。企图通过 (η5 EtO2 CC5H4 ) 2 Fe2 (CO) 4(5 )和硫黄制备 μ3 S立方烷簇合物 (η5 EtO2 CC5H4 ) 4Fe4 (μ3 S) 4(6 )未获成功 ,其中 5是由 η5 EtO2 CC5H4 Fe(CO) 2 Na与 η5 EtO2 CC5H4 Fe(CO) 2 I (4 )缩合制得。新化合物 1～ 5经元素分析 ,IR和1 HNMR光谱表征     

STRUCTURE OF (C_5H_7S_2) [Mo_3(μ_3-0) (μ-X)_3(μ-OAc)_3C1_3] (X=Cl,Br)

<正> Introduction. In order to synthesize trinuclear Mo cluster compounds with three bridge-linked acetoxyle groups, we changed the reaction condition described in reference(1) thus obtaining two new cluster compounds with the formula(C_5H_7S_2)[Mo_3(μ_3-O)(μ-X)_3(μ-OAc)_3Cl_3] (referred to beIow as compound (Ⅰ) when X=C1 and compound (Ⅱ) when X=Br). The diffraction work shows that the crystals of these two compounds are isomorphic.     

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.     

THE SYNTHESIS AND STRUCTURE OF Mo_3(μ_3-O)(μ-S)_3(μ-O_2CC_6H_5)_2(dtp)_2(Py)

<正> The title compound was prepared by reaction of Mo3(μ3-O) (μ-S)3-(dtp)4 (H2O) with C6H5COONa and pyridine. C27 H35 Mo3NO9P2S7, Mr = 1091.76, monoclinic, space group P21/c, a = 15. 057(5), b = 13. 052(5), c = 21. 662(6)(?), β=105.97(2)°, V = 4093(2) (?)3, Z = 4, Dc= 1. 77gcm-3, F(000) = 2176, μ(MoKα)=13.50cm-1, final R =0. 068 for 2835 observations. The molecular configuration is new and of approximate C, symmetry, and there are two C6H5COO bridging groups in the structure. The three Mo atoms form an isosceles triangle with three sides of 2. 567(3), 2. 576(3), and 2. 649(3)(?), where the two Mo-Mo bonds bridged by C6H5COO group are much shorter than that without. Something about the reactivity of Mo clusters is discussed.     

CRYSTAL STRUCTURE OF (C_5H_9C_5H_4)_3Er_4(μ_2-Cl)_6(μ_3-Cl)(μ_4-O)-(THF)_3

<正> The crystal of (C5H9C5H4)Er4(μ2-Cl)6(μ3-Cl)(μ4-O)(THF)3 belongs to triclinic space group P1, with a = 11. 909(4), b = 15.343(5), c=15. 619 (4)(?), α=104. 18(2), β=98. 81(3), γ= 111. 06(2)°, V = 2486(1)(?)3, Z = 2, Dc = 2. 07g/cm3, λ(MoKα) = 0.71073(?), μ= 73. 4cm-1, F(000) = 1476, Mr=1549. 25. The structure was solved by Patterson and Fourier techniques and refined by block diagonel least-squares method to final R = 0. 078 and Rw = 0. 084 for 5594 reflections with I≥1. 5σ(I). The results revealed that the complex is composed of four Er atoms bridged by seven Cl and one oxygen atoms with three of the Er atoms bonded each to a cyclopentylcyclopentadienyl group, and one Er atom, bonded to three THF. The Er atoms constitute a pseudo-tetrahedron.     

Further studies of the reactions of PtRu5(μ6-C)(CO)16 with alkynes: The preparation and structural characterizations of PtRu5(CO)13(μ-EtC2Et)(μ3-EtC2Et)(μ5-C) and Pt2Ru6(CO)17(μ-η5-Et4C5)(μ3-EtC2Et) (μ6-C)

The reaction of PtRu₅(CO)₁₆(μ₆-C),1 with 3-hexyne in the presence of UV irradiation produced two new electron-rich platinum-ruthenium cluster complexes PtRu₅(CO)₁₃(μ-EtC₂Et)(μ₃-EtC₂Et)(μ₅-C),2 (20% yield) and Pt₂Ru₆(CO)₁₇(μ-η⁵-Et₄C₅)(μ₃-EtC₂Et) (μ₆-C),3 (7% yield). Both compounds were characterized by single-crystal X-ray diffraction analyses. Compound2 contains of a platinum capped square pyramidal cluster of five ruthenium atoms with the carbido ligand located in the center of the square pyramid. A EtC₂Et ligand bridges one of the PtRu₂ triangles and the Ru-Pt bond between the apical ruthenium atom and the platinum cap. The structure of compound3 consists of an octahedral PtRu₅ cluster with an interstitial carbido ligand and a platinum atom capping one of the PtRu₂ triangles. There is an additional Ru(CO)₂ group extending from the platinum atom in the PtRu₅ cluster that contains a metallated tetraethylcyclopentadienyl ligand that bridges to the platinum capping group. There is also a EtC₂Et ligand bridging one of the PtRu₂ triangular faces to the capping platinum atom. Compounds2 and3 both contain two valence electrons more than the number predicted by conventional electron counting theories, and both also possess unusually long metal-metal bonds that may be related to these anomalous electron configurations. Crystal data for2, space group Pna2₁,a=19.951(3) Å,b=9.905(2) Å,c=17.180(2) Å,Z=2, 1844 reflections,R=0.036; for3, space group Pna2₁,α=13.339(1) Å,b=14.671(2) Å,c=11.748(2) Å, α=100.18(1)°, β=95.79(1)°, γ=83.671(9)°,Z=2, 3127 reflections,R=0.026.     

STRUCTURE OF TRANS-SYN-BIS-[(η-(CH_3)_2CHC_5H_4)Mo (μ-S)(μ-SC(CH_3)_3)]

<正> Mr = 648.75, triclinic, space group P1 , a = 10.087(4), b = 12.686(5), c = 14.222(6) A, α= 104.83(3)°, β = 124.61(4)°, γ = 90.98(3)°, V = 1417.22A3, Z = 2, De = 1.520 Mg.m-3, (MoKα)= 0.71069A, μ(MoKα) = 11.597 cm-1, F(000) = 664, room temperature. Final R=0.0424 for 5705 observed reflections. In the molecule two metal atoms are bonded togetherin a cavity surrounded by Ugands. Pour sulphur atoms are in bridging positions and in the same plane perpendicular to the metal-metal vector with the two t-butylthiolato ligands being in mutu-syn positions.     

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.     

Synthesis and structure of three isomeric cluster complexes (μ-H)Os3μ-O2CC5H4Mn(CO)3(PPh3)2(CO)8

The reaction of (μ-H)Os₃μ-O₂CC₅H₄Mn(CO)₃(CO)₁₀ with PPh₃ in the presence of Me₃NO gave mono- and disubstituted heterometallic complexes (μ-H)Os₃μ-O₂CC₅H₄Mn(CO)₃(PPh₃)(CO)₉ and (μ-H)Os₃μ-O₂CC₅H₄Mn(CO)₃ (PPh₃)₂(CO)₈. Crystal structure determination was performed for three isomeric cluster complexes (μ-H)Os₃μ-O₂CC₅H₄Mn(CO)₃(PPh₃)₂(CO)₈, which are both geometrical and conformational isomers differing in color. The geometrical isomerism is due to the attachment of the PPh₃ group at different vertices of the Os₃ triangle relative to the O₂CC₅H₄Mn(CO)₃ bridging ligand. The conform ational isomerism implies that the molecules have the same arrangement of ligands and differ only in the values of bond angles between the planar fragments of the clusters.     

Synthesis and characterization of tris(η~5-cyclopentadienyl-μ-carbonyliron)-μ_3-nitrosyl cluster:X-ray structure of[(η~5-C_5H_5)(μ-CO)Fe]_3(μ3-NO).C_4H_8O

Tris)(η 5-cyclopentadienyl-μ-carbonyl-iron)-μ3-nitrosyl cluster was obtained from the reaction of cyclopentadienyl dicarbonyliron dimer with nitrogen monoxide in xylene. The cluster was characterized by elemental analyses, IR, MS and 1H NMR. The crystal structure of [(η5-C5H5)(μ-CO)Fe]3(μ3-NO).C4H8O was determined by X-ray diffraction analysis. It crystallizes in the orthorhombic space group Pnma, a=9.053(2), 6=10.545(2), c=22.525(4) A, V=2150.3(7) A3, Z=4,Dc=1.68 g.cm-3; structure solution and refinement based on 1141 reflections with I > 3.0 (I) (MoKa, A=0.71073 A) converged at R=0.0540. The infrared absorption band at 1325 cm-1 of the μ3-NO in the cluster, which is red shifted, shows that μ3-NO is activated.     

SYNTHESIS AND CRYSTAL STRUCTURE OF DINUCLEAR IRON CARBONYL DERIVATIVE (μ-SC_6H_5) (μ-P (SC_6H_5)_2) Fe_2 (CO)_5 (P-(SC_6H_5)_3)

<正> The reaction of Fe3(CO)12 with P(SPh)3 yields the tile compound. C41H30Fe2O5P2S6, Mr = 968. 65, monoclinic, space group, P21/n, a = 14. 449(9), b = 18. 046(11), c=16.871(10)(?), β=98. 76°, V = 4348(?)3, Z = 4, Dc=1. 480g/ cm3, λ(MoKα) = 0. 71073(?) The structure was determined by direct methods and difference Fourier syntheses and refined by full-matrix least-squares procedure to R = 0.084, Rw = 0.144 for 4059 reflections. Fe(1)-Fe(2) = 2. 576(6), Fe(2)-P(2) = 2.194(9)(?). The dihedral angle between the Fe(l)SFe(2) and Fe(1)PFe(2) planes is 81. 9°. The other one (dihedral angle between SFe(1)P and SFe(2)P planes) is 75. 2°.     

[Li3DME][(η~5-C_5H_5)_3Nd(μ-H)Nd(η~5-C_5H_5)_3]的合成及其分子结构

标题配合物是以THF作溶剂,通过(C_5H_5)_2NdCl·ZLiCl和甲基萘钠的还原反应合成的。其晶体属单斜晶系,P 2/c空间群,晶胞参数α=9.235(2)A,b=11.695(2)A,c=20.810(3)A,β=92.88(1)°,Z=2。研究结果表明,标题配合物由相互不相联的〔Li3DME〕~ 和〔(η~5-C_5H_5)_3Nd(μ-H)Nd(η~5-C_5H_5)_3〕~-离子对组成。阳离子中,Li原子与由3个DME提供的6个O原子配位,形成八面体构型,Li—O平均键长为2.116A;阴离子中,2个Nd原子不直接键合,系通过桥H联接,Nd—H=2.19A。此外,每个Nd原子各有3个C_5H_5~-与之配位,Nd—C平均键长为2.812A。     

SYNTHESIS AND CRYSTAL STRUCTURE OF COMPLEX [CrMo_3 (μ_3-O)_3(μ-O)(μ-O_2CCH_3)_5(O_2CCH_3)_3]Na2 · H_2O

<正> The title complex C CrMo3 (μ3-O )3 (μ-O) (μ-O2CCH3 )5 (O2CCH3)3]2Na2 · H2O (Mr=1814. 32) crystallizes in monoclinic, space group P21/ n with a=11.209(5), b=18. 05(1), c=14. 44(1) A , β= 98. 30(5)°. V=2890 (3) A3, Z=2, A = 2. 08 g/cm3, F(000) -1780, Final R = 0. 049, Rw = 0. 058 for 2622 independent reflectons with I>3σ(I). The complex anion contains two Mo3O4 cores which connect two chromium atoms through four μ3-O atoms and eight bridging CH3COO- groups. Each of the Cr atoms and the Mo atoms is coordinated by six oxygen atoms. The anions are linked by Na cations to form one-dimensional infinite chain structure.     

New triosmium–iridium clusters: Synthesis and molecular structure of [Os3Ir2(Cp1)2(μ-OH)(μ-CO)2(CO)8Cl] (1), [Os3IrCp1(μ-OH)(CO)10Cl] (2), [Os3IrCp1(μ-H)(μ-Cl)(η3,μ3-C5H2N(NH2)Br)(CO)9] (3) and [Os3IrCp1(μ-Cl)2(η2,μ3-C5H3N(NH)Br)(CO)7] (4)

The trinuclear osmium carbonyl cluster, [Os₃(CO)₁₀(MeCN)₂], is allowed to react with 1 equiv. of [IrCp¹Cl₂]₂ (Cp¹ = pentamethylcyclopentadiene) in refluxing dichloromethane to give two new osmium–iridium mixed-metal clusters, [Os₃Ir₂(Cp¹)₂(μ-OH)(μ-CO)₂(CO)₈Cl] (1) and [Os₃IrCp¹(μ-OH)(CO)₁₀Cl] (2), in moderate yields. In the presence of a pyridyl ligand, [C₅H₃N(NH₂)Br], however, the products isolated are different. Two osmium–iridium clusters with different coordination modes of the pyridyl ligand are afforded, [Os₃IrCp¹(μ-H)(μ-Cl)(η³,μ₃-C₅H₂N(NH₂)Br)(CO)₉] (3) and [Os₃IrCp¹(μ-Cl)₂ (η²,μ₃-C₅H₃N(NH)Br)(CO)₇] (4). All of the new compounds are characterized by conventional spectroscopic methods, and their structures are determined by single-crystal X-ray diffraction analysis.     

Crystal structure of twinned (η5-C5(CH3)4CF3) (η5-C5(CH3)5)Ru

The substituted sandwich complex crystallizes in monoclinic space groupP2₁/m withZ=2. Twinning to the (001) direction with the special conditionc ^*/4a ^* = cos ^* causes systematic superposition of the reciprocal lattices of both domains and results in an apparent unit cell with double volume and the reflection condition (2h)kl, l=2n. The structure solution was obtained with the subset of intensity data for the predominant individuum and converged atR = 0.040,R _w =0.046 for 832 independent observations and 122 variables. The molecules show disorder with respect to the crystallographic mirror plane. The structure is closely related to that of decamethylruthenocene.