The Butterfly Selenato-bridged Cluster(μ-PhCH_2Se)_2Fe_2(CO)_6

1　ＩＮＴＲＯＤＵＣＴＩＯＮＲｅｃｅｎｔｙｅａｒｓｈａｖｅｗｉｔｎｅｓｓｅｄａｍａｒｋｅｄｉｎｃｒｅａｓｅｉｎｔｈｅｌｉｔｅｒａｔｕｒｅｉｎｔｈｅｕｓｅｏｆｓｅｌｅ ｎｉｕｍａｎｄｔｅｌｌｕｒｉｕｍａｓｂｒｉｄｇｉｎｇａｎｄｓｔａｂｉｌｉｚｉｎｇｌｉｇａｎｄｓｓｉｎｃｅｔｈｅｙｅｘｈｉｂｉｔｕｎｕｓｕａｌｓｔｒｕｃ ｔｕｒａｌａｎｄｒｅａｃｔｉｖｉｔｙｐａｔｔｅｒｎｓ.〔1〕Ｏｕｒｏｎｇｏｉｎｇｒｅｓｅａｒｃｈｐｒｏｇｒａｍａｉｍｅｄａｔｅｘｐｌｏｒｉｎｇｎｅｗｃｏｎｖｅｎｉｅｎｔｓｙｎｔｈｅｔｉｃ…     

Tetranuclear CuII Cluster as the Ten Node Building Unit for the Construction of a Metal–Organic Framework for Efficient C2H2/CO2 Separation

Rational design of high nuclear copper cluster-based metal–organic frameworks has not been established yet. Herein, we report a novel MOF ( FJU-112 ) with the ten-connected tetranuclear copper cluster [Cu₄(PO₃)₂(μ₂-H₂O)₂(CO₂)₄] as the node which was capped by the deprotonated organic ligand of H₄L (3,5-Dicarboxyphenylphosphonic acid). With BPE (1,2-Bis(4-pyridyl)ethane) as the pore partitioner, the pore spaces in the structure of FJU-112 were divided into several smaller cages and smaller windows for efficient gas adsorption and separation. FJU-112 exhibits a high separation performance for the C₂H₂/CO₂ separation, which were established by the temperature-dependent sorption isotherms and further confirmed by the lab-scale dynamic breakthrough experiments. The grand canonical Monte Carlo simulations (GCMC) studies show that its high C₂H₂/CO₂ separation performance is contributed to the strong π-complexation interactions between the C₂H₂ molecules and framework pore surfaces, leading to its more C₂H₂ uptakes over CO₂ molecules.     

Structural Regularities of the Transition Metal Complexes Containing o-Benzenedithiol (H_2bdt)——Synthesis and Structure of Fe_3(bdt)_3(PBu_3~n)_3

Complex Fe_3(bdt)_3(PBu_3~n)_3 was synthesized in the presence of PBu_3~n and the structural regularities in a series of transition metal complexes containing bdtH_2 ligand were summarized. The title complex crystallizes in the triclinic space group P-, Mr=1195.19, cell parameters: a=13.283(3), b=20.115(5), c=13.156(3), (?)=90.33(2), β= 116.47 (1), γ=92.19(2)°, V=3143.5(2.7)~3, Z=2, d_c=1.26g/cm~3. The structure was solved by direct methods from 4122 unique reflections with I>4σ(I) and reached the final convergence factor of R(Rw) = 0.053 (0.060). The complex exhibits strong paramagnetism.     

CRYSTAL STRUCTURE OF IRON CARBONYL-DIPHENYLACETYLENE DERIVATIVE,[Fe_2(CO)_6(PhC_2Ph)_2(CO)]

<正> M=664.21, onthorhombic, Pcab, a=10.434(3), b=19 .528(5), c=28.305 (5)A, V=5767.3A3, Dx=1.530 gcm-3, Z=8, λ(MoKα)=0.7107A. Final R=0.083, Rw= 0.078 for 2138 observed reflections. The complex(Fe2(CO)6(PhC2Ph)2(CO)) was structurally characterized. The Fe-Fe bond length is 2.537(2)A.     

Electronic Structure Calculation for Co_6(μ_6-C)(μ_3-S)_2(CO)_(12) Cluster

ItiswellAnownthametalclusterscontalninganintershhalnon-metalatomven'welImodelforcatalysisofcatalystSorotherphenomenonofsndcesciencef'-=].However.chermStSoftenpuzzleoverthefonnationmechanismandtheintershhalatom.Qfcourse'thehUemoleculeisoneexampleofthecase.Here.weattempttounderstandtheseprOblemsbytheelectronicStrUctUrecalculationOfthecluster.Themoleculargeometwofthecltistercomesfromx-ra}'theonanalysis1']ltbelongstoD3hp'mmetn'.ItisshowninFigUre1.H-Iineatondcorbital5wereadoptedforalIatoms.…     

Syntheses and Crystal Structures of Two New Iron-sulfur Carbonyl Complexes: [Fe_2(SC_6H_4Cl)_2(CO)_6]·0.5(Et_2O) and [Fe_3(SC_6H_4NH_2)_6(CO)_6]·2(MeOH)

Two new iron-sulfur carbonyl complexes, [Fe2(SC6H4Cl)2(CO)6]?0.5(Et2O) 1 and [Fe3(SC6H4NH2)6(CO)6]?2(MeOH) 2, have been prepared and characterized by elemental analysis, IR spectra and single-crystal X-ray diffraction. Crystal data for 1: monoclinic, C2/c, a = 18.4439(8), b = 11.0999(5), c = 25.1830(10) ?, β = 97.0370(10)o, V = 5116.8(4) ?3, Z = 8, C20H13Cl2Fe2O6.50S2, Mr = 604.02, Dc = 1.568 g/cm3, μ = 1.540 mm–1, F(000) = 2424, the final R = 0.0545 and wR = 0.1454 for 3443 observed reflections with I > 2σ(I); 2: monoclinic, P21/n, a = 12.350, b = 26.3050(11), c = 16.057 ?, β = 97.891(3)°, V = 5166.9(2) ?3, Z = 4, C44H44Fe3N6O8S6, Mr = 1144.76, Dc = 1.472 g/cm3, μ = 1.128 mm–1, F(000) = 2352, the final R = 0.0442 and wR = 0.1197 for 7978 observed reflections with I > 2σ(I). Complex 1 contains one iron dimer, in which two tricarbonyliron(I) fragments are bridged together by two 4-chlorophenylthiolate ligands, whereas complex 2 contains a linear tri-iron cluster, in which two terminal tricarbonyliron(II) fragments and the central Fe(II) atom are linked together by six 4-aminophenylthiolate bridging ligands.     

A New Ionic Trimolybdenum Cluster Compound:〔Mo_3S_7(S_2P(iprO)_2)_3〕〔S_2P(iprO)_2〕

1INTRODUCTIoNInthepastdecades,thechemistryofMo-Sclusterscontaininga[Mo,(p,-S)(p-S,),j corehasbeenstudiedtextensively,andmanysuchkindofcompoundshavebeensynthesized.(1'2'3'4iHowever,fewcompoundscontainingadiscreteclus-tercationhavebeenreported.[5iInthispaper,wereportthesynthesisandstructureofthetitlecompound.Thisisanewexampleoftrimolybdenumclustercontainingadiscreteclustercation.2EXPERIMENTALAllmanipulationwerecarriedoutinair.2.1Synthesis0f[M0,S,(S,P(iprO),),jtS,P(iprO),jAmixture…     

Study on the Magnetic Properties of MoFe_3S_4 Single Cubane－like Clusters Containing R_2dtc Ligands

ＳｔｕｄｙｏｎｔｈｅＭａｇｎｅｔｉｃＰｒｏｐｅｒｔｉｅｓｏｆＭｏＦｅ_３Ｓ_４ＳｉｎｇｌｅＣｕｂａｎｅ－ｌｉｋｅＣｌｕｓｔｅｒｓＣｏｎｔａｉｎｉｎｇＲ_２ｄｔｃＬｉｇａｎｄｓＬＩＵＱｉｕ－Ｔｉａｎ；ＤＥＮＧＹｕ－Ｈｅｎｇ；ＣＨＥＮＣｈａｎｇ－Ｎｅｎｇ（?..     

Structure and Nonlinear Optical Property of the Cluster Compound V_2S_6O_2Cu_6（3-MePy）_6

A cluster compound V2S6O2Cu6(3-MePy)6(3-MePy = 3-methyl pyridine) has been synthesized by using skiving method and the crystal structure was characterized by X-raydiffraction: space group P1, Z = 1, a = 9.7278(4), b = 10.4180(5), c = 11.9230(6) , α = 108.240(3), β = 98.120(2), γ = 99.500(2)o, R = 0.052 and wR = 0.104. The NLO properties were studied by Z-scan technique with 8 ns pulsed laser at 532 nm. The cluster exhibits strong NLO absorptive ability(α2 = 1.7 × 10–10 m·W–1) and effective self-focusing performance(n2 = 1.27×10–18 m2·W–1) in a 1.58 × 10–4 mol·dm–3 DMF solution.     

(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:     

[μ-PhC(O)S](μ-RS)Fe_2(CO)_6与(μ-R~1S)(μ-XMgS)Fe_2(CO)_6新奇反应的研究——孪合簇合物[(μ-RS)Fe_2(CO)_6](μ_4-S)[μ-R~1S)Fe_2(CO)_6]的合成、鉴定及形成机理

通过(μ-RS)(μ-XMgS)Fe_2(CO)_6与PhC(O)Cl反应合成了4个新苯甲酰配合物[μ-PhC(O)S](μ-RS)Fe_2(CO)_6(R=Me,Et,n—Bu,CH_2=CHCH_2). 它们进一步与(μ-R~1S)(μ-XMgS)Fe_2(CO)_6反应得8个不同 R,R~1基的孪合簇合物[(μ-RS)Fe_2(CO)_6](μ_4-S)[(μ-R~1S)Fe_2(CO)_6].其中R=n-Bu,R~1=Ph的配合物经X射线单晶结构分析表明是由1个μ_4-S将2个碎片PhS Fe_2(CO)_6及n-BuSFe_2(CO)_6螺结在一起的.其空间群为P—1; a=9.028(3),b=10.386(1),c=16.723(5)A;α=87.70(2),β=75.67(2),γ=82.26(2)°; Z=2; D_x=1.743g/cm~3.最终偏离因子R=0.031.     

Synthesis and Characterization of Tetrametal Cluster〔Co_2(CO)_6〕〔μ-HC_2CH_2OCH_2C_2H-μ〕〔Co_2(CO)_6〕

１ＩＮＴＲＯＤＵＣＴＩＯＮＩｎｔｅｎｓｅｉｎｔｅｒｅｓｔｉｎｔｒａｎｓｉｔｉｏｎ ｍｅｔａｌｃｌｕｓｔｅｒｓｃｏｎｔｉｎｕｅｓｂｅｃａｕｓｅｔｈｅｙｒｅｐｒｅｓｅｎｔｐｏｓ ｓｉｂｌｅｃｏｎｃｅｐｔｕａｌｂｒｉｄｇｅｓｂｅｔｗｅｅｎｈｏｍｏｇｅｎｅｏ...     

Solvothermal Syntheses of (H_2en)_2Sn_2S_6·en and[(H_2hmda)_3(Hhmda)_2](Sn_2S_6)_2Using SnCl_4 and S_8 as Starting Materials

1 INTRODUCTION Since Bedard et al. reported microporous tin(IV) sulfides synthesized by hydrothermal method in the presence of organic amine in 1989[1, 2], a number of thiostannates have been synthesized using hydro- or solvothermal techniques with organic amines as tem- plates. The structures of the resulting tin(IV) sulfi- des are related to the types of organic amines. Two- dimensional polyanions of the types of [Sn3S7]2- and [Sn4S9]2-, which are denoted as SnS-1 and SnS-3, respe…     

Reactions of [Et_3NH][(μ-CO)(μ-RS)Fe_2(CO)_6] with acetylenes.Synthesis of(μ-σ,π-p-MeC_6H_4C=CHPh)(M-RS)Fe_2(CO)_6 and (μ-σ,π-PhC=CHC_6H_4Me-p)(μ-RS)Fe_2(CO)_6 The crystal structure of (μ-σ,π-p-MeC_6H_4C=CHPh)(μ-tBuS)Fe_2(CO)_6

The reactions of [Bt3NH][μ-CO)(μ-RS)Fe2(CO)6] (1a-d) (R=nPr,nBu,tBu, Ph) with p-MeC6H4C=CPh or m-NO2C6H4C=CPh were studied and products of the vinyl type (μ-σ,π-p-MeC6H4C=CHPh)(μ-RS)Fe2(CO)6 (2) and (μ-σ,π-phC=CHC6H4Me-p) (μ-RS)Fe2(CO)6 (3) (R=nPr, nBu, tBu, Ph) were obtained. While the structures of all the compounds 2a-d and 3a-d were characterized by elemental analysis, IR,1H NMR and MS spectroscopies, the single-crystal structure of 2c(R=tBu) was determined by X-ray diffraction method. The X-ray dim-action result of 2c showed that the substituted vinyl ligand p-MeC6H4C=CHPh bridges the two uon centers, being σ-bonded to one metal through the olefinic carbon attached to p-MeC6H44 group, while π-bonded to the other via olefinic linkage; the Fe2(CO)6 and proton units are in a cis fashion and the tBu group is bonded to sulfur atom through an e-type of bond.     

A NOVEL REACTION BETWEEN [μ-PhC(O)S]-(μ-RS)Fe_2(CO)_6 AND (μ-R~1S)(μ-XMgS)Fe_2(CO)_6——THE SYNTHESIS, CHARACTERIZATION AND FORMATION MECHANISM OF TWIN CLUSTER COMPLEXES [(μ-RS)Fe_2(CO)_6](μ_4-S)[(μ-R~1S)Fe_2(CO)_6]

The reaction of (μ-RS)(μ-XMgS)Fe_2(CO)_6 with PhC(O)Cl gave four new benzoyl complexes [μ-PhC(O)S](μ-RS)Fe_2(CO)_6(R=Me, Et, n-Bu, CH_2=CHCH_2), which further reacted with (μ-R~1S)(μ-XMgS)Fe_2(CO)_6 to afford eight new twin cluster complexes with the general formula of [(μ-RS)Fe_2(CO)_6](μ_4-S)[(μ-R~1S)Fe_2(CO)_6]. The single crystal X-ray analysis for one of these complexes (R=n-Bu, R~1=Ph) showed that it consists of two different moieties PhSFe_2(CO)_6 and n-BuSFe_2(CO)_6 joined together through the spiran type of μ_4-S., The complex belongs to space group P-1; cell parameters are a=9.028(3), b=10.386(1), c=16.723 (5); α=87.70(2)°,β=75.67(2)°, r=82.26(2)°; z=2, Dx=1.743 g/cm~3. Final deviation factor R=0.031.     

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 STRUCTURE OF (Et_4N)_3[Mo_2Fe_6S_8(SPH)_9]

<正> Introduction. A series Of Mo-Fe-S complexes with doublecubane structure has been synthesized and identified. Because of the similarity of its extended X-ray absorption fine structure (EXAFS) to that of FeMo cofactor and nitrogenase, suggestion has been made that the doublecubane complexes may serve as models for the Mo site of nitrogenase. Therefore, the investigation of this type of complexes has attracted much attention. By using the similar method of spontaeous self-assembly reaction, and starting from certain kinds of Mo-Fe-S compounds, we have been able to obtain several kinds of compounds, one of which     

铁硫原子簇配合物(μ-MeS)[μ-Fe(CO)_2CpS]Fe_2(CO)_6的晶体和分子结构

标题化合物为单斜晶系,空间群P2_1/n,晶胞参数:a=7.9099(7),b=10.774(1),c=22.531(4)A,γ=92.91(1)°,Z=4.本文讨论了铁硫原子簇配合物(μ-R~1S)(μ-R~2S)Fe_2(CO)_6中,取代基R~1,R~2大小对化合物结构的影响。当R为较大的基团,如PPh_3或Fe(CO)_2Cp时,平均Fe-S键增长.而且簇骨架外的Fe-S键增长比簇骨架内的Fe-S键增长更加明显,说明Fe-Fe键有稳定骨架的作用.R基团的大小对簇骨架内的扭角S-Fe-Fe-S也有明显的影响。标题化合物中R~1,R~2取代基采取(a,e)构象排布,有利于缓解取代基间的空间排斥作用。     

Synthesis and Crystal Structure of Cluster 〔C_6H_4-1,2-(CO_2CH_2C_2H-μ)_2〕〔Co_2(CO)_6〕_2

１ＩＮＴＲＯＤＵＣＴＩＯＮＯｃｔａｃａｒｂｏｎｙｌｄｉｃｏｂａｌｔｉｓａｖｅｒｙｃｏｎｖｅｎｉｅｎｔｓｔａｒｔｉｎｇｍａｔｅｒｉａｌｆｏｒｔｈｅｐｒｅｐａｒａｔｉｏｎｏｆａｌｍｏｓｔａｎｙｃｏｂａｌｔｃｏｍｐｏｕｎｄ〔１〕．Ｔｈｅｒｅａｃｔｉｏｎｓｏ...