STRUCTURAL STUDIES OF THE COPPER(II) ACETATE COMPLEXES Cu(o2CCH3)2(pyridine)3 AND Cu6(μ-O2CCH3)4(μ4-O2CCH3)2(μ-OCMe3)6

Abstract

[Cu(O₂CCH₃)₂]₂, 1, reacts with pyridine to form violet-blue Cu(O₂CCH₃)₂(pyridine)₃, 2, in > 90% yield. 2 crystallizes from pyridine with a distorted square-pyramidal geometry around copper with the monodentate acetate ligands located diagonally in the basal positions. 1 reacts with Bi(OCMe₃)₃ in THF to form blue Cu₆(μ-O₂CCH₃)₄(μ₄-O₂CCH₃)₂(μ-OCMe₃)₆, 3. 3 crystallizes from THF/hexanes with a hexagon of copper atoms linked by six doubly-bridging tert-butoxide ligands, four doubly-bridging bidentate acetates, and two quadruply-bridging bidentate acetate ligands.     

CRYSTAL STRUCTURE OF Mo_3(μ3-S)_2(μ-Cl)_3[S_2P(OEt)_2]_3

<正> M=1013.98, hexagonal, P63/m, a=b=15.492(2), c=8.530(4)A, γ=120°, V=1773A3, Z=2, Dc=1.899°g.cm-3. Final R=0.042 for 611 reflections.This is a Bl(bicapped) type trinuclear molybdenum cluster with two S capping atoms located on the 63 axis and exhibits full D3h symmetry. The Mo-Mo distances are 2.606(1)A, with a bond order of 11/3. It is paramagnetic.     

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 Mo_3(μ_3-O) (μ-S_2)_ 3 [S_2P(OEt)_2]_3I

<正> Mr=1178.9, monoclinic, P21/n, a=16.570(2), b=12.370(1), c=20.007(2) A,β=99.97(1)°, V=4039.0A3, Z=4, Dx=1.938 Mgm-3, λ(MoKα)=0.7107A, μ(MoKα)=23.96 F(000)=2296, room temperature. Final R value=0.047 for 4387 unique observed reflections. It consists of neutral mono-oxo-capped trinuclear molybdenum cluster molecules with an average Mo-Mo bond length of 2.626(4)A and an average Mo-0 bond length of 2.036(2)8.     

Synthesis and Structure of the Complex [Mo3(μ3-S)(μ2-S2)3(Et2NCS2)3 +Br-

Tri-₂-disulfido-₃-thiotris(diethyldithiocarbamato)-S,S'-triangle-trimolybdenum bromide [Mo₃(₃-S)(₂-S₂)₃(Et₂NCS₂)₃ ⁺Br^- was obtained and characterized.     

Co3(CO)7(μ3-S)(μ,η2-SCNR2)的合成和晶体结构

Co2(CO)8与4个二硫代双(烷基硫代甲酰胺)类前配体[R2NC(S)S]2反应,得4个含烷基硫代甲酰胺基的三核钴羰基硫簇合物.通过元素分析、IR、1H NMR和MS等方法表征了它们的结构,用X射线衍射法测定了其中一个簇合物Co3(CO)7(μ3-S)[μ,η2-SCN(i-Pr)2](Ⅲ)的晶体结构.晶体属单斜晶系,P21/n空间群,晶胞参数a=1.145 2(2)nm,b=1.502 8(3)nm,c=1.2144(2)nm,a=90°,β=92.15(3)°,γ=90°,V=2.088 5(7)nm3,Z=4,F(000)=1 096,Dc=1.747 mg·m-3,GOF(F2)=0.835,μ=2.588 nm-1.最终因子R[I＞2σ(I)]=0.040 7,Rw=0.062 4.     

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.     

THE STRUCTURE OF TRIS(PYRIDINUM)(μ_3-SULFIDO)-TRIS(μ-DISULFIDO)-HEPTA-CHLORO-TRIMOLYBDENUM, (PyH)_3[Mo_3(μ_3-S)(μ-S_2)_3Cl_7]·1/2H_2O

<正> M=1101.86, cubic, Pa3, a=19.605(2), V=7533(3)A3, Z=8, Dc=1.943 g.cm-3. Final R=0.041 for 1120 reflections. The cluster anion is a mono(μ3-S) capped trinuclear species with each Mo atom having a distorted pentagonal bipyramidal coordination. A striking feature of this anion, which sharply differs from [Mo3S13] 2-,2 is the existence of a Cl atom connecting three S atoms by covalent bond to some extent.     

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 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.     

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。     

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.     

盖帽三核钴羰基簇合物(μ_3-CH_3C)Co_3(CO)_7(μ-PPh_2CH_2PPh_2)和(μ_3-CH_3C)Co_3(CO)_9的质谱研究

本文从结构化学角度,阐述了标题化合物的EI质谱断裂行为。这些化合物的分子离子基本上按分步断裂分别失去羰基,直至获得[CH_3CCo_3(PPh_2CH_2PPh_2)]~+和[CH_3CCo_3]~+。然后,这些残基和含膦配体继续断裂,失去Ph、PhP、Ph_3P、C_7H_7、C_6H_6、C_2H_2、H_2和Co等,生成各种相应的三核、二核和单核钴的碎片离子。     

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.     

1,2,4-Triphospholyl gold(I) and copper(I) complexes: synthesis,crystal and molecular structures of [Cu(PMe3)2(μ-P3C2tBu2)(μ-I)Cu(PMe3)2], [Cu(PMe3)2(μ-P3C2tBu2)2Cu(PMe3)2] and [Au(η1-P3C2tBu2)2][Au(PEt3)2]

Treatment of K(P₃C₂^tBu₂) with Cu₂I₂ and PMe₃ gave the binuclear complex [Cu(PMe₃)₂(μ-P₃C₂^tBu₂)₂Cu(PMe₃)₂] via the isolated intermediate compound [Cu(PMe₃)₂(μ-P₃C₂^tBu₂)(μ-I)Cu(PMe₃)₂]. The reaction of K(P₃C₂^tBu₂) with [AuCl(PEt₃)] on the otherhand gave the cation:anion complex [Au(PEt₃)₂][Au(η¹-P₃C₂^tBu₂)₂]. All complexes were fully characterised by multinuclear spectroscopy and single crystal X-ray diffraction studies.     

Synthesis and characterization by diffraction and 31P- and 77Se-NMR spectroscopy of [Mo3(μ3-Se)(μ2-Se2)3{N(SePPh2)2}3]Br and [Mo3(μ3-Se)(μ2-Se2)3{Se2P(OCH2CH3)2}3]Br

The new Mo/Se clusters [Mo₃(μ₃-Se)(μ₂-Se₂)₃{N(SePPh₂)₂}₃]Br (1) and [Mo₃(μ₃-Se)(μ₂-Se₂)₃{Se₂P(OCH₂CH₃)₂}₃]Br (2) have been synthesized by the selective substitution of the bromo ligands in the starting material [PPh₄]₂[Mo₃(μ₃-Se)(μ₂-Se₂)₃Br₆] with the selenoorgano bidentate ligands [N(SePPh₂)₂]^– and [Se₂P(OEt)₂]^–. The complexes have been characterized in solution by ³¹P- and ⁷⁷Se-NMR spectroscopy and in the solid state by single crystal X-ray diffraction; the same cation structures are present both in solution and in the solid state. Crystallographic data for 1: [Mo₃(μ₃-Se)(μ₂-Se₂)₃{N(SePPh₂)₂}₃]Br·3 CH₂Cl₂, C₇₂H₆₀BrMo₃N₃P₆Se₁₃·3 CH₂Cl₂, trigonal, space group R₃, a=21.299 (10) Å, c=38.433 (27) Å, V=15 100 (15) ų, T=−120 °C, Z=6; crystallographic data for 2: Mo₃(μ₃-Se)(μ₂-Se₂)₃{Se₂P(OCH₂CH₃)₂}₃]Br, C₁₂H₃₀BrMo₃P₃O₃Se₁₃, monoclinic, space group P2₁/n, a=13.404 (2) Å, b=22.732 (4) Å, c=13.932 (3) Å, β=113.134 (3)°, V=3 903.7(12) ų, T=−120 °C, Z=4. © 2000 Académie des sciences / Éditions scientifiques et médicales Elsevier SASphosphine ligands / amine ligands / phosphate ligands / selenium / molybdenum cluster / ⁷⁷Se-NMR spectroscopy     

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.