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1.
Activity on catalytic reduction of C_2H_2 for seven Mo-Fe-S cluster compounds (I. (Et_4N_4)_4[Mo_2Fe_2S_(10)]·2CH_3OH, Ⅱ. Mo_2Fe_2S_4(S_2CNEt_2)_5·CH_3CN, Ⅲ. (Bu_4N)_3 [Mo_2FeS_8O]·Ⅳ·(Et_4N)_3[Mo_2FeS_8O_2], V. (Et_4N)_2[MoFeS_4(SCN)_2(OCH_3)_2]·3CH_3OH, Ⅵ. (Et_4N)_3[Mo_2FeS_8O(OCH_3)_2], Ⅶ. (Et_4N)_4Mo_2Fe_7S_(12)(SPh)_6·6CH_3OH), three Fe-S cluster compounds (Ⅷ.(Et_4N)_2[Fe_4S_4(S_2CNEt_2)_4], Ⅸ. (Bu_4N)_2[Fe_4S_3(SC(CH_3)_3)_4], Ⅹ. (Bu_4N)[Fe_2S_3(SCH_2Ph)_2]) and combination systems of related compounds, has been determined under anaerobic conditions at 25℃ and with KBH_4 as the reductant. In addition, at 15℃, under otherwise the same conditions, activity on catalytic reduction of C_2H_2 for different constituent systems from (NH_4)_2MoS_4 and FeCl_3 has also been determined.  相似文献   

2.
由贫硫化合物{Mo_3S_4[S_2P(OEt)_2]_4·H_2O}通过加硫获得了富硫化合物{Mo_3S_7[S_2P(OEt)_2]_3·I}(CH_8C_6H_5).化合物属三斜晶系,空间群PI,晶胞参数为a=10.350(1)A,b=13.931(4)A,c=16.369(3)A,α=103.69(2),β=86.62(1),γ=111.99(2)°,V=2183A~3;z=2,D_c=1.817g·cm~(-3).最终结构偏离因子R为0.042. 簇分子{Mo_3(μ_3-S)(μ-S_2)_3[S_2P(OEt)_2]3·I}属{Mo_3(μ3一Y)(μ-S_2)_3[S_2P(OEt)_2]_3·X}(Y=O,S;X=Cl,I)系列构型.{Mo_3}基本上是一个正三角形,Mo—Mo键长分别为2.721(1),2.724(1),2.725(1)A,Mo的配位多面体为七个硫原子组成的畸变五角双锥,有一个I原子联结着三个(S_2)~(2-)桥基的三个不与Mo共平面的S原子,I—S距离平均为3.169A,比相应的Van der Waals距离(~4.00A)明显地短,显示一定程度的成键作用,簇分子的这一构型是一种较为稳定的结构类型.  相似文献   

3.
在无氧非水介质中,以(NH_4)_2MoS_4,FeCl_3和NaS_2CNEt_2为原料合成了簇合物 [Mo_2Fe_2S_4(S_2CNEt_2)_5]·CH_3CN.X射线单晶结构测定表明,它具有[Mo_2Fe_2S_4]~(5+)类立方烷核心骨架。每个金属原子有一螯合基团S_2CNEt_2配位。第五个S_2CNEt_2基团在两个Mo原子间跨桥配位。XPS和Mossbauer谱的测定及M-S(M=Fe或Mo)键长比较表明,簇合物中Fe原子的氧化态是不同的,而两个Mo原子则具有相同的氧化态。该簇合物为顺磁性物质,μ_m=4.27μ_B。此外,还测定了它的红外光谱,紫外-可见光谱和催化乙炔还原活性。  相似文献   

4.
本文总结了作者们研究一系列两核和三核钼原子簇化合物的结果。这些化合物是三核原子簇: (C_5H_7S_2)_3[Mo_3(μ_3-S)_2(μ_2-Cl)_3Cl_6] (Ⅰ); (C_5H_7S_2)_3[Mo_3(μ_3-S)(μ_2-S_2)_3Cl_7] (Ⅱ); Mo_3(μ_3-S)(μ_2-S_2)_3[S_2P(OEt)_2)_3Cl (Ⅲ); (Et_4N)_2[Mo_3(μ_3-O)(μ_2-Cl)_3(Oac)_2Cl_5] (Ⅳ); (C_5H_7S_2)[Mo_3(μ_3-O)(μ_2-Cl)_3(Oac)_3Cl_3] (Ⅴ); 和两核原子簇: (C_5H_7S_2)_3[Mo_2Cl_9] (Ⅵ); M0_2S_4[S_2P(OEt)_2]_2 (Ⅶ)。 本文的第一部分简要地介绍了这些化合物的合成方法。第二部分扼要地给出了这些化合物的晶体与分子结构。簇合物Ⅰ是离子型结构,簇阴离子是双(S)帽三核原子簇,每个Mo原子周围为八面体六配位,Mo—Mo间距为2.617。簇阴离子Ⅱ和簇分子Ⅲ均是单(S)帽三核簇,Mo原子周围为畸变五角双锥构型,Mo—Mo键长分别为2.751和2.725。簇阴离子Ⅳ和Ⅴ均是单(O)帽三核簇,Mo原子周围的配位为畸变八面体,Mo—Mo键长分别为2.597和2.577。化合物Ⅵ是三(μ_2—Cl)桥两核原子簇,其构型为两个共面八面体,Mo—Mo间距为2.707。化合物Ⅶ为双(S)桥两核原子簇,Mo原子周围为四角锥配位,Mo—Mo键长为2.828。 本文的第三部分用简化分子轨道方法分析了三种主要类型的三核钼原子簇中Mo_3体系的M—M键?  相似文献   

5.
The title compound was prepared by the reaction of Mo_3S_4(dtp)_4(H_2O)[ctp=S_2P(OEt)_2]with NaOAc·3H_2O and C_4H_8NCS_2NH_4.Crystallographic data:[Mo_3(μ_3-S)(μ-S)_2(μ-OAc)-(S_2CNC_4H_8)_3(O)_2]·0.5CH_2CI_2·2H_2O,Mr=980.18,triclinic,space group P,α=12.360(3),b=16.653(6),c=9.206(2)A,α=101.97(2),β=108.32(2),γ=86.14(3)°.V=1759.6(9)A~3,Z=2,Dc=1.85 g/cm~3,F(000)=962,μ(Mo K_α)=16.53 cm~(-1).Final R=0.044 for 4301 reflections with I≥3σ(I).This compoundmay be regarded as a mixed-valent trinuclear molybdenum cluster{Mo_2(V)Mo(Ⅳ)(μ_3-S)(μ-S)_2-(μ-OAc)(S_2CNC_4H_8)_3(O)_2}.The Mo-Mo distances are 2.783(1),2.833(1)and 3.374(2)A in the Mo_3non-equilateral triangle and there exist only two Mo-Mo bonds.The cluster was obtained by oxi-dation and ligand substitution of{Mo_3(μ_3-S)(μ-S)_3[μ-S_2P(OEt_2)][S_2P(OEt)_2]_3(H_2O)}.  相似文献   

6.
文献报道的三钼簇合物大多是配位对称的,而配位不对称的(包括配位空缺或称为配位不饱和的)在化学上更有意义,但报道甚少。最近我们合成了“松散”配位的三核钼簇合物若干个,其中簇合物{Mo_3(μ_3-S)(μ-S)_3[S_2P·(OEt)_2]_4(H_2O)}(1)和{Mo_3(μ_3-X)(μ-S)_3[S_2P·(OEt)_2]_4·SC(NH_2)_2}(2 X=1/2O+1/2S),已用X射线衍射法测定了晶体结构,发现不对称配位的Mo—L键较通常的长,显得“松散”,配基L可以被其他π-型中性配基置换,在化学上  相似文献   

7.
The reaction of Mo(0) complex [Mo(CO)_4(S_2CNEt_2)]~- with phenthiolate [Et_4N]SΦin acetonitrilo in the presence of small amount of air affords a new oxo-molybdenum com-plex [MoO(SΦ)_2(S_2CNEt_2)]~-,which crystallizes in two forms of crystals,[Et_4N][MoO(SΦ)_2(S_2CNEt_2)](1a) and [Et_4N][MoO(SΦ)_2(S_2CNEt_2)]·(CH_3)_2CHOH (1b).The structures of1a and 1b were determined from three-dimensional X-ray data.1a crystallizes in the mo-noclinie,space group C_c with a=12.321(4),b=15.245(4),c=16.087(9);β=98.44(4)°.V=2989~3,Z=4,D_c=1.35 g/cm~3 and R=0.031 for 2434 reflections [I>3(I)].1b crystallizes inthe monoclinic,space group P2_1/n with a=9.861(1),b=20.357(3),c=17.122(5)A;β=92.27(2)°,V=3434.3~3,Z=4;D_c=1.29 g/cm~3 and R=0.051 for 2852 independeut reflections [I>3σ(I)],The structures of 1a and 1b reveal that the anion [MoO(SΦ)_2(S_2CNEt_2)]~- contains asingle oxo ligand coordinating to a molybdenum(Ⅳ) and the geometry around Me(Ⅳ) atomis a distorted square pyramid.Interestingly,the solvate molecule isopropanol of 1b is linkedto oxo group by a hydrogen-bond of 1.928A,leading to the increase of Mo=O bond distance(1.718).Mo—S distances are 2.44 and 2,39.The electrochemical behavior of 1 wasdiscussed also.  相似文献   

8.
测定了Mo_4(μ_(3-)O)_2O_4Cl_2(O_2CC_6H_5)_6和Mo_4(μ_(3-)O)_2O_4Cl_2(O_2CC_6H_4CH_3)_6·2C_6H_5Cl四钼簇合物在N,N-二甲基甲酰胺溶液中的循环伏安特性、电子吸收光谱、固体粉末样品的表面光电压谱和光声光谱。讨论Mo_2(V)结构单元中弱M—M键的特性,认定了Mo—Mo键前线区域轨道的对称标号。  相似文献   

9.
S~(2-)作为配位方式多变的配位基,已为人们所知,而以S_4~(2-)为配位基的钼化合物,现在还为数不多。我们合成的[Mo_2S_8O_2]~(2-)不仅含有S_2~(2-)、S_4~(2-)基,还含有端基氧,其结构是很有趣的。混合(NH_4)_6Mo_7O_(24)·4H_2O和NH_2OH·HCl的水溶液,与K_2S反应后,用(CH_3)_4NBr沉淀,产物再用丙酮和DMF混合液重结晶,得[(CH_3)_4N]_2[Mo_2S_8O_2]的极薄的橙色片状晶体。其元素组成是:Mo 30.7,S40.5,C15.6,N4.3,H4.0(%);计算值为:Mo30.4,S40.8,C15.3,N4.6,H3.9(%)。  相似文献   

10.
分别通过Mo≡Mo→Mo≡Mo的双电子氧化还原反应及由单核Mo(Ⅲ)配合物经硫脲[SC(NH_2)_2]桥联的方法合成具有三重Mo—Mo键的配合物Mo_2Cl_5[SC(NH_2)_2]_3·2H_O.该配合物晶体的结晶学参数为:三斜晶系,PI空间群,.晶胞中2个结晶学独立的分子中Mo—Mo键长分别为2.439(1)A和2.443(1)A.配合物的S-C键削弱了桥S原子参与d-p相互作用的程度,有利于形成较强的Mo≡Mo键,其d-d分子轨道的电子构型是ν~2(π+δ)~4.  相似文献   

11.
<正> The cluster compound Mo3S4[S2P(OEt)2]4(H2O) with a comparatively stable cluster core [Mo3(μ3-S)(μ-S)3]4+ and some labile ligands or loosely coordination sites has been already prepared successfully by a self-assembly reaction. Its surprising chemical reactivity in the reactions of substitution, addition, and oxidation has been noted and used widely for the syntheses of a series of new, trinuclear Mo cluster compounds, of which the structures of the 12 selected compounds characterized by X-ray diffraction analysis are exhibited in diagrams. Meanwhile, those compounds with the same cluster core [Mo3(μ3-S)(μ-S)2]4+ show two groups of characteristic IR bands at ~480 cm-1 for the Mo-(μ-S) vibration and -450cm-1. for the Mo- (μ3-S), and their selected bond distances are tabulated as well.In a cluster-catalyzed homogeneous process, it is important that clusters have loose coordination sites or are coordination unsaturated. In our further research on the medium-valence molybdenum clusters[1], we have foun  相似文献   

12.
Emerald green crystals of a new mixed-valence oxochloromolybdenum complex,Mo(OH)2(2,2′-bipy)Cl2.[MoO(2,2′-bipy)Cl3]2, were obtained in an attempt to synthesize the Mo-S cluster compounds under solvothermal conditions. The title compound was characterized by EPR and X-ray single-crystal diffraction techniques. Crystallographic data: orthorhombic, space group Fdd2, a = 12.684(1), b = 21.518(2), c = 29.096(3)A, Mr = 1103.97, V= 7941(1)A^3, Z= 8, Dc =1.843 g/cm^3,μ= 1.514 mm^-1, F(000) = 4304, R = 0.0654 and wR = 0.1544 for 1944 observed reflections with 1 ≥/ 2σ(I). The compound consists of two different neutral molecules, Mo^IV-(OH)2(2,2′-bipy)Cl2 and MoVO(2,2′-bipy)Cl3. Both Mo^IV and Mo^V ions are in a distorted octahedral environment. The Mo(1)^IV atom is surrounded by two Cl^- ions and two O atoms from OH^- and two N atoms from a 2,2′-bipy ligand. The Mo(2) atom is surrounded by three Cl^- ions, one O^2- anion and two N atoms from another 2,2“-bipy ligand. The bipyridine occupies two cis-equatorial sites, while the Cl^- ions are located at the axial and equatorial positions.  相似文献   

13.
The highly unusual Mo(VI) thioether complexes [MoO(2)X(2)(L-L)][space](X = Cl or Br; L-L = MeS(CH(2))(2)SMe or EtS(CH(2))(2)SEt) were obtained by reaction of MoO(2)X(2) with L-L in rigorously anhydrous CH(2)Cl(2) solution. Similar reaction of MoO(2)Cl(2) with the diselenoether MeSe(CH(2))(2)SeMe gives the very reactive [MoO(2)Cl(2)[MeSe(CH(2))(2)SeMe]] as a yellow solid. These compounds are very moisture sensitive and were characterised by IR, diffuse reflectance UV-vis and multinuclear ((1)H, (13)C[(1)H], (77)Se and (95)Mo) NMR spectroscopy. The data are consistent with distorted 6-coordination at Mo(vi)viatrans X ligands, mutually cis oxo groups and a chelating dithio- or diseleno-ether ligand. Variable temperature (1)H and (13)C[(1)H] NMR data indicate fast pyramidal inversion at the coordinated chalcogen atoms occurs at room temperature, but cooling slows this process to reveal resonances consistent with the meso and dl forms. The (95)Mo NMR spectra are single resonances in the region 200-300 ppm, as expected for Mo(vi) complexes, and show inverse dependence of the chemical shifts upon both halide and chalcogen type. Crystal structures of three of the dithioether complexes are described and provide unequivocal evidence for Mo(vi) thioether coordination, confirming chelation of the dithioether through long Mo-S interactions of ca. 2.7 [Angstrom]. Attempts to extend the range of compounds by using other chalcogenoether ligands failed, indicating that to obtain complexes involving these extremely mis-matched metal ligand combinations requires both the favourable 5-membered chelate ring and small terminal alkyl substituents on the chalcogen.  相似文献   

14.
离子型有机锡化合物的合成及其生物活性   总被引:2,自引:1,他引:1  
钟桂云  孙丽娟 《应用化学》2011,28(4):387-393
利用有机锡卤化物与有机酸在有机胺存在下反应合成了一系列离子型有机锡化合物,分子通式为[HNR3][(PhCH2)3Sn(μ2-SCH2COO)Cl]、[HNR3][Ph3Sn)3(O2CCH2CO2)2]·CH3CH2OH和[HNR3] [MeCy2ClSnO2CCH2CO2SnClCy2Me]。化合物的体外抗肿瘤、杀菌和杀螨活性测试结果表明,部分化合物具有很好的生物活性。[HNR3][(Ph3Sn)3(O2CCH2CO2)2]·CH3CH2OH和[HNR3] [MeCy2ClSnO2CCH2CO2SnClCy2Me]配合物对人肺癌细胞株A-549、结肠癌细胞株HCT-8和肝癌细胞株Bel-7402的抑制率约为90%,[HNR3][MeCy2ClSnO2CCH2CO2SnClCy2Me]配合物对小麦赤霉、番茄早疫、芦笋茎枯、苹果轮纹、花生褐斑的杀死率都为100%,配合物[HNR3] [MeCy2ClSnO2CCH2CO2SnClCy2Me]的杀螨活性致死率大于90%。  相似文献   

15.
Reactions of [ReH5(PMe2Ph)3] with alkynols HC≡CC(OH)(R)C≡CSiMe3 (R=tBu, iPr, 1‐adamantyl) in the presence of HCl give the vinylcarbyne complexes [Re{≡CCH?C(R)C≡CSiMe3}Cl2(PMe2Ph)3], which react with tBuMgCl to give [Re{≡CCH?C(R)C≡CSiMe3}HCl(PMe2Ph)3]. Treatment of [Re{≡CCH?C(R)C≡CSiMe3}HCl(PMe2Ph)3] with nBu4NF gives [Re{≡CCH?C(R)C≡CH}HCl(PMe2Ph)3], which first isomerizes to the bicyclic complexes [Re{CH?CH? C(R)?CCH?}Cl(PMe2Ph)3], and then to the rhenabenzynes [Re{≡CCH?C(R)CH?CH}Cl(PMe2Ph)3]. The NMR spectroscopic and structural data as well as the aromatic stabilization energy (ASE) and nucleus‐independent chemical‐shift (NICS) values suggest that these rhenabenzynes have aromatic character.  相似文献   

16.
二(三)丁基锡烯基(炔基)膦酸酯的合成与表征   总被引:7,自引:0,他引:7  
合成了12个新的二(三)丁基锡烯基(炔基)膦酸酯[(n-C4H9)nSn]n-1O2P(0)R,并用元素分析,红外光谱,核磁共振氢谱和TG-DTA对其组成和结构进行了表征,初步生物活性测试表明,有些化合物具有较强的杀螨和杀菌活性。  相似文献   

17.
The oxygen-bridged, silicon-substituted alkane {(Me3Si)2CH(SiMe2)}2O (1) may be prepared by the reaction of {(Me3Si)2CH}Li with ClSiMe2OSiMe2Cl in refluxing THF. Similarly, the alkane {(Me3Si)(Me2MeOSi)CH(SiMe2CH2)}2 (2) is readily accessible from the reaction between {(Me3Si)(Me2MeOSi)CH}Li and ClSiMe2CH2CH2SiMe2Cl under the same conditions. Compound 1 reacts with two equivalents of MeK to give the polymeric complex [[{(Me3Si)2C(SiMe2)}2O]K2(OEt2)]infinity [5(OEt2)] after recrystallisation. Treatment of 2 with two equivalents of either MeLi or MeK gives the corresponding complexes [{(Me3Si)(Me2MeOSi)C(SiMe2CH2)}2Li][Li(DME)3] [7(DME)3] and [{(Me3Si)(Me2MeOSi)C(SiMe2CH2)}2K2]n (8), respectively, after recrystallisation. Treatment of the alkane (Me3Si)2(Me2MeOSi)CH with one equivalent of MeK gives the polymeric complex [{(Me3Si)2(Me2MeOSi)C}K]infinity (3). These compounds have been identified by 1H and 13C{1H} NMR spectroscopy and elemental analyses and compounds 5(OEt2), 7(DME)3 and 3 have been further characterised by X-ray crystallography. Compound 7(DME)3 crystallises as a solvent-separated ion pair, whereas 5(OEt2) and 3 adopt polymeric structures in the solid state.  相似文献   

18.
The 12‐membered‐ring metallacycles [mer‐Re{≡CCH=C(R)C≡C?}Cl(PMe2Ph)3)]2 (R=CMe3, 1‐adamantyl), which are organometallic analogues of antiaromatic octadehydro[12]annulene, are prepared by heating the methyl carbyne complexes mer‐Re{≡CCH=C(R)C≡CH}(CH3)Cl(PMe2Ph)3. An intermolecular σ‐bond metathesis between the Re?CH3 bond and the acetylenic C?H bond is proposed for their formation.  相似文献   

19.
Zhang  Hong  Lin  Ran  Luo  Ming  Xia  HaiPing 《中国科学:化学(英文版)》2010,53(9):1978-1981

This paper presents a new convenient route to prepare osmafuran starting from readily accessible HC≡CCH(OH)C≡CH and OsHCl(CO)(PPh3)3. Treatment of a solution of OsHCl(CO)(PPh3)3 in dichloromethane with HC≡CCH(OH)C≡CH, followed by the addition of acetic acid, produced osmafuran [Os(CHC(PPh3)CO(CH2CH3))Cl(CO)(PPh3)2]Cl (2). 2 has been isolated in good yield and fully characterized. 1H and 13C NMR spectra show the characteristic downfield chemical shifts of the ring hydrogen and carbon atoms. NMR and X-ray diffraction data provide strong evidence for the aromatic nature of 2. Probably due to the effect of the phosphonium substituent, 2 exhibits remarkable thermal stability, air stability and lower reactivity.

  相似文献   

20.
Addition of [Mo(V)2O2S2(edt)2]2- (edt =1,2-ethanedithiolate) to acetonitrile and/or methanol solutions of MnII containing bipyridines [4,4'-trimethylenedipyridine (TDP), 4,4'-bipyridine (4,4'-bpy), 2,2'-bipyridine (2,2'-bpy)] or 15-crown-5 produces three new heterometallic cluster coordination polymers, [Mn2[Mo2O2S2(edt)2]2(TDP)3(CH3OH)2(NCMe)2].3CH3OH.0.25MeCN (1), [Mn(TDP)2(H2O)2]2+[Mn[Mo2O2S2(edt)2)2(TDP)2]]2-.6CH3OH (2), [Mn[Mo2O2S2(edt)2](TDP)2(CH3OH)(H2O)].CH3OH (3), and three new multinuclear clusters, [Mn[Mo2O2S2(edt)2](4,4'-bpy)(CH3OH)4].0.5(4,4'-bpy) (4), [Mn[Mo2O2S2(edt)2](2,2'-bpy)2].2CH3OH (5), and (NEt4)2[Mn(15-crown-5)[Mo2O2S2(edt)2]2] (6). All compounds were characterized by X-ray crystallography. The coordination mode of Mn in these compounds depends on the ligands and the crystallization conditions. Compound 2 readily converts to 1 or 3 depending on the reaction and solvent conditions. Compounds 1 and 2 were analyzed using thermogravimetric analysis combined with mass spectroscopy (TG-MS) in the temperature range 25-500 degrees C. The room-temperature magnetic moments for compounds 1-6 were determined.  相似文献   

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