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.     

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。     

(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.     

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。     

Synthesis of Palladium Clusters with the P--N--P Assembling Ligands (Ph2P)2CH2 (dppm) and (Ph2P)2NH (dppa). Crystal Structure of [Pd4(μ-Cl)2(μ-dppm)2(μ-dppa)2](PF6)2

Tetrapalladium clusters containing dppa or dppa and dppm bridging ligands were prepared by condensation of dinuclear units. Reaction of [Pd₂Cl₂(-dppa)₂] with [Cu(PPh₃)]PF₆ (generated in situ in THF) yielded [Pd₄(-Cl)₂(-dppa)₄] (PF₆)₂ (4) in a virtually quantitative yield but [Pd₄(-Cl)₂(-dppm)₂(-dppa)₂] (PF₆)₂ (6) was best prepared in CH₂Cl₂ from [Pd₂Cl₂(-dppm)₂] and [Pd₂(MeCN)₂(-dppa)₂](PF₆)₂ (2). The structure of 6·2(CH₃)₂CO·2H₂O was determined by X-ray diffraction. It consists of a planar, centrosymmetric 10-membered ring structure. The four bridging diphosphine ligands are of two types: two dppa ligands support the Pd Pd bonds [2.6055(4) Å], whereas the two dppm ligands bridge between two palladium atoms separated by 3.722(4) Å, which are also bridged by a chloride ligand.     

A New Preparation of Mo2(CO)8(μ-PPh2)2 and W2(CO)8(μ-PPh2)2 by a Phosphorus-Carbon Bond Cleavage Reaction. Crystal Structure of a New Polymorph of Mo2(CO)8(μ-PPh2)2

A new synthesis of Mo₂(CO)₈(-PPh₂)₂ and W₂(CO)₈(-PPh₂)₂ by the reaction of molybdenum and tungsten hexacarbonyls with a tetraazamacrocyclic ligand containing —CH₂PPh₂ side chains, comprising cleavage of the phosphorus-methylene bond has been performed. The complexes have been investigated by magnetic and spectroscopic measurements and by single-crystal structure analyses. The structural characterization of a new polymorph of Mo₂(CO)₈(-PPh₂)₂ has been described.     

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 (Br(μ-Met)(μ-Gly)(H_2O)_4]_2[Er(μ-Net)_2(H_2O)_4]_2(ClO_4)_(12)

<正> [Er(u-Met)(u-Gly)(H2O)4]2[Er(u-Met)2(HaO)4]2(ClO4)12(NMet=CH3S-(CH2)2CH(NH2)COOH,Gly=NH2CH2COOH), Mr=3194, trilinic, space group P1, a = 12.375(6),b= 14.041(13), c=19.074(13)A,α=80.85(6),β=80.72(6).γ=62.82(6)° ,Z=1,V= 2896A3,Dc=1.83 g/cm3,R=0.091. The carboxyl groups of Met and Gly in the title complex are bonded to Er atoms as bidentate bridging ligands.There are two different cations located at crystallographic symmetry centers in one unit cell.     

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.     

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     

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.     

Hydrothermal synthesis and characterization of LaIII and CuII coordination polymers with 5-nitroisophthalic acid (H2Nip), [La2(μ-Nip)(μ-SO4)2(H2O)5] n and {[Cu3(μ-OH)2(μ-Nip)2(μ-H2O)2] · 2H2O} n

3D La^III and 2D Cu^II coordination polymers with 5-nitroisophthalate anions, [La₂(μ-Nip)(μ-SO₄)₂(H₂O)₅] _n (1) and {[Cu₃(μ-OH)₂(μ-Nip)₂(μ-H₂O)₂] ·?2H₂O} _n (2), have been synthesized, characterized and studied by X-ray crystallography. The La atoms have eight–coordinate geometries in distorted square antiprism environments and the Cu atoms have five- and six–coordinate geometries with distorted square pyramidal and octahedral environments. Self-assembly of these compounds in the solid state occurs through coordination and hydrogen bonding.     

Formation of mixed-metal alkoxides mediated by the reactivity of coordinated pinacol: Synthesis and molecular structures of Ce2Ti2(μ3-O)2(μ,η2-OCMe2CMe2O)4(OPri)4(PriOH)2 and of Ce2Nb2(μ3-O)2(μ,η2-OCMe2CMe2O)4(OPri)6

The addition of pinacol to mixtures of titanium and cerium isopropoxides as well as the use of insoluble titanium and cerium pinacolate synthons was investigated as a route to M-Ce (M=Ti, Nb) species. Pinacol was able to promote the formation of mixed-metal species and the first Ce-Ti and Ce-Nb species namely Ce_2Ti(pin)₂(OPrⁱ)₈ and [M₂Ce₂(μ₃-O)₂(μ,η²pin)₄(OPrⁱ)₆H_x] [M=Ti, x=2; M=Nb, x=0; pin=OCMe₂-COMe₂] were isolated and characterized by FT-IR and ¹H NMR. The latter were also characterized by X-Ray diffraction. Their structures are based on a rhombus compressed along the M⋯M direction with 6-coordinated metals. The pinacolate moieties act as bridging-chelating ligands. The metal–oxygen bond lengths vary according to M–O(pin)<M-μ₃–O<Mμ–O(pin)<Ce–OPrⁱ<Ce–μ₃O.     

Syntheses and characterization of the vanadium trimer (V3(μ3-O)O2)(μ2-O2P(CH2C6H5)2)6(4,4′-bipyridine) and the vanadium hexamer [(V3(μ3-O)O2)(μ2-O2P(CH2C6H5)2)6]2(μ2-N1,N2-di(pyridin-4-yl)oxalamide)

Reacting VO(acac)₂ with six equivalents of dibenzylphosphinic acid in the presence of 4,4′-bipyridine or μ₂-N¹,N²-di(pyridin-4-yl)oxalamide leads to trimeric (V₃(μ₃-O)O₂)(μ₂-O₂P(CH₂C₆H₅)₂)₆(4,4′-bipyridine) or the hexamer [(V₃(μ₃-O)O₂)(μ₂-O₂P(CH₂C₆H₅)₂)₆]₂(μ₂-N¹,N²-di(pyridin-4-yl)oxalamide). The complexes were characterized by spectroscopic (FTIR and ¹H NMR spectroscopies), TGA, and by single crystal X-ray diffraction measurements. The structures consist of a planar central core where three vanadium ions are arranged in the form of a quasi-isosceles triangle and contain an interstitial O which is multiply bonded to one V and weakly interacting at different bond distances to the remaining two V ions.     

Silver(I) ion induced formation of 2-D ternary lead(II)-silver(I)-4-tolythiolate [PbAg2(μ-Stol)2(μ4-Stol)2]n from 1-D binary lead(II)-4-tolythiolate [(μ-Cl)Pb2(Stol)(μ-Stol)2]n (tol = 4-tolyl)

Treatment of [Pb(Stol)₂]_n with an equiv of [Et₄N]Cl in DMF afforded a new 1-D polymeric complex, [(μ-Cl)Pb₂(Stol)(μ-Stol)₂]_n (1), with Pb–Cl–Pb links. Interaction of 1 with a suspension of [Ag(Stol)] in DMF resulted in formation of a 2-D polymeric complex, [PbAg₂(μ-Stol)₂(μ₄-Stol)₂]_n (2), with the planar four-membered Ag₂S₂ and PbAgS₂ rings bridged by μ-Stol and μ₄-Stol ligands. Both polymeric complexes were structurally characterized by single-crystal X-ray diffraction analysis.     

Synthesis and X-ray crystal structure of the electron-deficient metal carbonyl cluster [Os3(CO)5(μ3-H)(μ-H)(μ-PtBu2)2(μ-Ph2PCH2PPh2)]

The reaction of [Os₃(CO)₁₀(μ-dppm)] (1) with ^tBu₂PH in refluxing diglyme results in the electron-deficient metal cluster complex [Os₃(CO)₅(μ₃-H)(μ-P^tBu₂)₂(μ-dppm)] (2) (dppm = Ph₂PCH₂PPh₂) in good yields. The molecular structure of 2 has been established by a single crystal X-ray structure analysis. In contrast to the known homologue [Ru₃(μ-CO)(CO)₄(μ₃-H)(μ-H)(μ-P^tBu₂)₂(μ-dppm)] (3), no bridging carbonyl ligand was found in 2. The electronically unsaturated cluster 2 does not react with carbon monoxide under elevated pressure, therefore 2 seems to be coordinatively saturated by reason of the high steric demands of the phosphido ligands.     

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.     

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.     

Tetranuclear azido-bridged copper(II) complex [Cu4(μ-salpn)2(μ1,1-N3)2(N3)2(H2O)2]: Synthesis,characterization and crystal structure

The reaction of salpnH₂ Schiff-base ligand (salpnH₂ = N,N′-bis(salicylidene)-1,3-propylenediamine) with Cu(NO₃)₂·3H₂O and a large excess of NaN₃ (1:2:8 molar ration), lead to the formation of [Cu₄(μ-salpn)₂(μ_1,1-N₃)₂(N₃)₂(H₂O)₂] (1), which has been successfully obtained and characterized by elemental analyses, IR spectroscopy and single-crystal X-ray diffraction. The strong absorption band at about 2000–2100 cm^?1 and at 1597 cm^?1 regions of the IR spectrum of 1 clearly proves the presence of the both end-on (EO) bridging and terminal azido ions and CN (azomethine) groups, respectively. Single-crystal X-ray analyses revealed that the copper atoms are bridged alternately by end-to-on (EO) azido and phenoxo-salpn ligands in the prepared tetranuclear copper(II) complex [Cu₄(μ-salpn)₂(μ_1,1-N₃)₂(N₃)₂(H₂O)₂] (1).     

(μ-RS)(μ-XMgS)Fe_2(CO)_6亲核性能的研究 铁硫配合物(μ-RS)[μ-CpFe(CO)_2S]Fe_2(CO)_6的合成及鉴定

(μ-RS)(μ-XMgS)Fe_2(CO)_6(A),是一类含活泼硫镁键的铁硫配合物.它与卤代烃、酰卤能发生亲核取代反应,与α,β-不饱和有机物发生共轭加成反应.然而它同有机过渡金属卤化物的反应至今未见报道.本文考察了配合物A与π-环戊二烯二羰基碘化铁的反应,首次制得通式为(B)的一系列含有机铁硫桥的非对称配合物.其反应式如下: