Mo~2S~4[S~2CNC~4H~8]~2的合成、结构表征及其与Cu^+,Ni^2+的反应

由(NH~4)~2Mo~2S~12H~2O和(NH~4)(S~2CNC~4H~8)在PPh~3参与反应下,获得Mo~2S~4(S~2CNC~4H~8)~2化合物,对此二核钼簇合物进行了红外、电子光谱、电化学及单晶X射线结构表征,并尝试与多种金属化合物进行[2+1]反应,从反应产物的晶体结构分析发现了包括金属夺取端基S^2-形成Mo~2O~2S~2(S~2CNC~4H~8)~2化合物,Cu^+被氧化并夺取配体(S~2CNC~4H~8)^-形成Cu(S~2CNC~4H~8)~2以及Mo(V)还原为Mo(IV),S^2-氧化为(S~2)^2-而形成Mo~3(μ~3-S)(μ-S~2)~3[S~2CNC~4H~8]~3.     

钼过氧配合物与HSO 在酸性溶液中的反应动力学和机理

用载流法研究了Mo~4O~12(O~2) [简作Mo~4(O~2)~2] 与HSO 在酸性条件(4×10^-3～0.5mol·dm^-3)下的反应动力学,并提出了反应机理.反应经历下列历程:Mo~4(O~2)~2+H~2O Mo~4(O~2)(OOH)(k~1,k~-1) Mo~4(O~2)(OOH)+HSO Mo~4(O~2)OOSO~2+H~2O(k~2,k~-2) Mo~4(O~2)OOSO~2+H~2O Mo~4(O~2)+H~2SO~4(k~1,k~-1)中间产物Mo~4(O~2)再以相同机理继续与HSO 反应.由机理,得到了[S(IV)/k~观察与[H^+],[S(IV)]之间的线性关系式以及20℃时的动力学参数:K~1=7.4±0.3dm^3·mol^-1·S^-1,k~-1/k~2=(5.8±0.5)×10^-2和k~-2/k~3=(1.4×0.8)×10^-4.配合物Mo~4(O~2)~2中(O~2)基质子化是决定反应速度的关键步骤.用此机理讨论了Thompson研究的 MoO(O~2)~2与HSO 的反应结果.     

钼过氧配合物与HSO 在酸性溶液中的反应动力学和机理

用载流法研究了Mo~4O~12(O~2) [简作Mo~4(O~2)~2] 与HSO 在酸性条件(4×10^-3～0.5mol·dm^-3)下的反应动力学,并提出了反应机理.反应经历下列历程:Mo~4(O~2)~2+H~2O Mo~4(O~2)(OOH)(k~1,k~-1) Mo~4(O~2)(OOH)+HSO Mo~4(O~2)OOSO~2+H~2O(k~2,k~-2) Mo~4(O~2)OOSO~2+H~2O Mo~4(O~2)+H~2SO~4(k~1,k~-1)中间产物Mo~4(O~2)再以相同机理继续与HSO 反应.由机理,得到了[S(IV)/k~观察与[H^+],[S(IV)]之间的线性关系式以及20℃时的动力学参数:K~1=7.4±0.3dm^3·mol^-1·S^-1,k~-1/k~2=(5.8±0.5)×10^-2和k~-2/k~3=(1.4×0.8)×10^-4.配合物Mo~4(O~2)~2中(O~2)基质子化是决定反应速度的关键步骤.用此机理讨论了Thompson研究的 MoO(O~2)~2与HSO 的反应结果.     

两个具有[Mo~3M'S~4]^5^+(M'=Mo,W)簇芯的原子簇化合物的合 成和晶体结构

以Mo~3S~4(dtp)~4.H~2O和M'(CO)~6(M'=Mo,W)为起始物在羧酸介质下通过[3+1]模式合成,分别得到一个同核和一个异核四核簇[Mo~4S~4(μ-C~2H~5CO~2)~2(dtpH)(dtp)~3]4和[Mo~3WS~4(μ-CH~3CO~2)~2(dtpH)(dtp)~3]5[dtp=(EtO)~2PS~2^-;dtpH=(EtO)~2P(S)(SH)]。两个簇合物以单晶X射线分析和IR谱学进行结构表征,它们均具有[M~4S~4]^5^+类立方烷簇芯。     

含羧基的三核钼原子簇

本文总结了作者研究的一组合有羧基的三核钼原子簇的结果。这些簇合物分为两类。第一类有: (C_2H_5)_4N[Mo_3(μ_3-O)(μ-O_2CH)_3(μ-Cl)_3Cl_3] (Ⅰ) (CH_3)_4N[Mo_3(μ_3-O)(μ-O_2CH)_3(μ-Cl)_3Cl_3] (Ⅱ) (CH_3)_4N[Mo_3(μ_3-O)(μ-O_2CH)_3(μ-Br)_3Cl_3] (Ⅲ) (C_5H_7S_2)[Mo_3(μ_3-O)(μ-O_2CCH_3)_3(μ-Cl)_3Cl_3] (Ⅳ) (C_5H_7S_2)[Mo_3(μ_3-O)(μ-O_2CCH_3)_3(μ-Br)_3Cl_3] (Ⅴ) (C_2H_5)_4N[Mo_3(μ_3-O)(μ-O_3CCH_3)(μ-Cl)_3X_3] (Ⅵ) (X为Cl和Br统计分布的簇合物) (C_2H_5)_4N[Mo_3(μ_3-O)(μ-O_2CCH_2CH_3)_3(μ-Cl)_3Cl_3] (Ⅶ) (C_2H_5)_4N[Mo_3(μ-O)(μ-O_2CCH_2CH_2CH_3)_3(μ-Cl)_3Cl_3] (Ⅷ) (Ⅰ)-(Ⅷ)的簇阴离子具有下述通式: [Mo_3(μ_3-O)(μ-O_2CR)_3(μ-X)_3X_3~′]~-; R=H,CH_3,CH_3CH_3,CH_2CH_2CH_2:X和X′=Cl或Br。 属于第二类型的目前只有一个,即: [(C_2H_5)_4N]_2[Mo_3(μ_3-O)(μ-O_2CCH_3)_2(μ-Cl)_3Cl_5) (Ⅸ) 本文将扼要介绍这些簇合物的合成方法,晶体和分子结构的主要特征,并对成簇规律、结构变化规律以及μ_3-O的红外光谱的指认,给予简单的讨论。     

新型Mo-Pb-S异四核簇合物 [Mo~3(PbI~3)S~4(dtp)~3(C~3H~4N~2)~3][(CH~3) ~2CO]~2 的合成和晶体结构

由[Mo~3(μ~3-O)(μ-S)~3(dtp)~4(H~2O)和PbI~3^-在咪唑存在下反应获得异四核混合簇[Mo~3(PbI~3)S~4(dtp)~3(C~3H~4N~2)~3][(CH~3)~2CO]~2(2)[dtp=S~2P(OC~2H~5)~2^-]。簇合物属斜方晶系,空间群P~b~c~a(No.61),晶胞参数为a=2.3590(3),b=1.9161(5),c=2.6458(9)nm,V=11.959(6)nm^3,Z=8。结构最终偏离因子R=0.067。此四核簇分子具有[Mo~3PbS~4]类立方烷簇芯,簇分子整体对称性接近C~3~v。在同一不对称单元中,簇分子的咪唑环以(NH)和溶剂丙酮分子的氧原子形成O---H---N氢键。     

从P-Mo(Ⅴ)杂多化合物合成多形貌Al_(13)基钼酸盐晶体

以H3PMo12O4·0nH2O、H4PMo11VO4·0nH2O和(NH4)6P2Mo18O6·2nH2O3种杂多化合物为钼源,采用直接混合后陈化的方法合成了多形貌A113基钼酸盐晶体,相应A113基钼酸盐晶体的形貌和尺寸分别是斜方三棱柱形(80μm×30μm)、星形(30μm×10μm)和叶片形(500μm×150μm)。粉末X射线衍射结果表明这3种多形貌A113基钼酸盐晶体结晶较好,在2θ为6.65°、8.00°和14.16°处都有强而尖锐的衍射峰。而以Na2MoO4·2H2O为钼源时只能制得无定形簇合物。根据ICP、FTIR和TG/DTG结果给出多形貌的Al13基钼酸盐晶体的化学简式为Na[AlO4Al12(OH)24(H2O)12][MoO4]·48H2O。初步探讨了A113基钼酸盐晶体的形成机理。     

三核钼原子簇化合物的EPR和电子结构

本文报道一个新的三核钼原子簇化合物在室温和77K固态和液态的EPR谱,这些谱均呈现出a,b两套谱线的叠加,分析谱线的强度比,线宽和谱参数,认为g值较大的a谱归属于三核钼原子簇化合物,而b谱归属于单核钼杂质。从由X射线晶体结构方法确定的空间结构出发,三核钼原子簇化合物可能有两种分子形式:Mo3(μ3-S)(μ2-S)3Cl[S2P(OEt)2]4 1Mo3(μ3-S)(μ2-S)(μ2-Cl)2Cl[S2P(OEt)2]4 2分别用简单量子化学理论和EHMO法计算出未配对电子所处的分子轨道,求出g1和g1,并与EPR实验值相比较,认为该化合物的分子式应为2,簇骼{Mo3}属七电子体系,在77K温度下,其未配对电子主要局域在三个钼原子所组成的近似等腰三角形簇骼的顶点钼原子周围。     

氢还原下铁钼催化剂的表面性质

用XPS对H_2还原下的铁钼催化剂的表面性质进行了研究。实验表明:H_2还原使表面钼离子由Mo~(6+)还原为Mo~(5+)和Mo~(4+),并与Fe~(3+)作用氧化为Mo~(6+);Fe~(3+)则由于与Mo~(5+)和Mo~(4+)作用以及H_2还原而变为Fe~(2+),从而形成了一个没有O_2存在,仅有H_2作用下的Mars-Krevelen氧化还原循环过程。在催化剂表面上生成的FeMoO_4,其Mo~(6+)的3d3/2和3d5/2的结合能值比Fe_2(MoO_4)_3中的Mo~(6+)的3d能级结合能值低。Mo(或Mo和Fe)离子键合的O~(2-)与H_2作用生成的Mo(Fe)-OH,其Os结合能的测定值低于键合于Mo(Fe)离子中的O~(2-)的Os结合能值,并且该结合能峰由于-OH间的相互作用结合成的水的脱附而消失。此外.给出了还原过程中H_2与催化剂表面O~(2-)相互作用的反应图式。     

钼簇合物反应性能的研究-SbCl3和具有松散配位三核钼簇合物的加合反应及其产物的晶体结构

报道具有松散配位的三核钼簇合物{Mo3(μ3-S)(μ-S)3[S2P(OEt)2]4.L(L'=H2O,C3H3ON,和SbCl3在HCl-EtOH中加合反应及其产物{Mo3(μ3-S)[(μ-S)3.SbCl3].[S2P(OEt)2]4(C2H5OH)}(C2H5OH)和{Mo3(μ3-S)[(μ-S)3.SbCl3][S2P(OEt)2]3[SXP(OEt)2].(C3H3ON)}(X=S,O)的晶体结构。结构测定结果表明,这两个加合物的分子由{Mo3(μ3-S)(μ-S)3[S2P(OEt)2]4.L(L=C2H5OH,C3H3ON)通过三个(μ-S)联结SbCl3而成,从而获得了{Mo3SbS4}的类立方烷簇胳构型,Sb一S之间存在较弱的配位键, 由此推断,若加合的金属原子的轨道和电子组态适宜,有可能通过这种[3+1]的成簇模式获得四核的同核或异核簇合物。     

Synthesis and characterization of three tetranuclear clusters containing a [Mo3OS3Sn]6+ cubane-like core

Three heterometallic cubane-like clusters, [Mo3(mu 3-O)(mu 3-S)3(SnCl3)(dtp)3(py)3] (dtp = S2P(OC2H5)2-, py = C5H5N) (1), (PPN)[Mo3(mu 3-O)(mu 3-S)3(SnCl3)(dtp)3(mu-OAc)(py)] (OAc = CH3COO-, PPN = (C6H5)3PNP(C6H5)3+) (2), and (Et4N)[Mo3(mu 3-O)(mu 3-S)3(SnCl3)(dtp)2(mu-OAc)2(py)] (3) have been prepared by the reaction of [Mo3(mu 3-O)-(mu-S)3(dtp)4(H2O)] (4), [Mo3(mu 3-O)(mu-S)3(dtp)3(OAc) (py)] (5), and [Mo3(mu 3-O)(mu-S)3(dtp)2(OAc)2 (py)] (6) with SnCl2, respectively. They have been characterized by IR, UV-vis, 31P NMR, 95Mo NMR, and X-ray structure analysis. All of these heterometallic clusters have a [Mo3OS3Sn]6+ core but contain a different arrangement of peripheral ligands. As far as the neutral cluster 1 is concerned, there is no bridging OAc ligand, while only one bridging OAc ligand is observed for cluster 2 and two are for cluster 3. The Mo-Mo distances are about 0.03-0.04 A shorter than those of the starting trimolybdenum clusters. This indicates that the incorporation of SnCl3- fragment into (Mo3) clusters makes the Mo-Mo bonding enhanced. Crystal data for 1: triclinic, space group P-1, a = 10.7423(2) A, b = 14.0357(1) A, c = 16.9346(2) A, alpha = 84.054(1) degrees, beta = 87.095(1) degrees, gamma = 84.517(1) degrees, V = 2525.82(6) A3, Z = 2, R = 0.038 for 5584 reflections (I > 2.0 sigma(I)). Crystal data for 2: triclinic, space group P-1, a = 12.9529(1) A, b = 15.6324(2) A, c = 19.6355(1) A, alpha = 92.083(1) degrees, beta = 97.908(1) degrees, gamma = 110.337(1) degrees, V = 3677.41(6) A3, Z = 2, R = 0.034 for 8665 reflections (I > 2.0 sigma(I)). Crystal data for 3: monoclinic, space group P2(1)/n, a = 14.0852(5) A, b = 15.1324(5) A, c = 23.2691(7) A, beta = 97.371(1) degrees, V = 4918.7(3) A3, Z = 4, R = 0.049 for 4970 reflections (I > 2.0 sigma(I)).     

Synthesis and Crystal Structure of α-Mo4XS3(μ-dtp)3(dtp)3 (X=0.6S + 0.4O)

The title compound (Mo4XS15P6O12C24H30), α-Mo4XS3(μ-dtp)3(dtp)3 (X=0.6S+0.4O; dtp=-S2P[OEt]2), isolated as a prismatic black crystal, was prepared from ethanolic solution of Mo(CO)6, MoCl5 and P2S5. It crystallizes in triclinic system, space group P with a=14.031(4), b=13.372(2), c=16.270(8)(A), α=92.15(2), β = 72.91(3), γ = 95.20(2)°, V = 2905.4(2)(A)3, Z = 2, Dc = 1.82 g/cm3, Mr=1598.93, F(000)=1564.8, λ=0.71069(A)(MoKα), μ=1.584 mm-1. The final R=0.058, Rw=0.057 for 5016 observed reflections with I≥3.0σ(I). The structure analysis reveals that the title compound has a [Mo4XS3] core, belonging to the cubane-type tetranuclear molybdenum clusters family, with one of its four μ3-caps being statistically occupied by S and O. Three dtp ligands chelated three μ-X capped Mo atoms as terminal ligands, while another three dtp bridged these three Mo atoms and the fourth one, forming an α-type cluster compound.     

Syntheses and Crystal Structures of Molybdenum-Sulfur Clusters Mo_3S_4 (dtp)_3(o-CH_3OC_6H_4COO)(Py) and Mo_3S_4 (dtp)_3(p-HOC_6H_4COO)(DMF)·EtOH

1 INTRODUCTION Recent years have seen a drastic increase of compounds containing the Mo3S4 core. A major synthetic route to these compounds is by the reaction of the aqua ion [Mo3S4(H2O)9]4+ with different kinds of ligands replacing some or all of the water molecules. In this way, Mo3S4(dtp)4(H2O), which was synthesized by the spontaneous- assembly method in 1986[1] and its structural characterization and chemical reactivity have been well recognized [2], can be rationally synthesize…     

Modeling the Formation of Molybdenum Oxides from Alkoxides: Crystal Structures of [Mo(4)O(4)Cl(4)(&mgr;(2)-OEt)(4)(HOEt)(2)(&mgr;(3)-O)(2)] and [PPN](+)[Et(3)NH](+)[Cl(2)(O)Mo(&mgr;(2)-O)(2)Mo(O)Cl(2)](2)(-)

The reactions of the binuclear oxomolybdenum(V) complex [Cl(2)(O)Mo(&mgr;-OEt)(2)(&mgr;-HOEt)Mo(O)Cl(2)] (1) with Me(3)Si(allyl) and SbF(3) produce the compounds [Mo(6)O(6)Cl(6)(&mgr;(3)-O)(2)(&mgr;(2)-OEt)(6)(&mgr;(2)-Cl)(2)] (2) and [Mo(8)O(8)Cl(6)(&mgr;(3)-O)(4)(OH)(2)(&mgr;(2)-OH)(4)(&mgr;(2)-OEt)(4)(HOEt)(4)] (3), respectively. Treatment of 1 with the Lewis base PMe(3) affords the tetrameric complex [Mo(4)O(4)Cl(4)(&mgr;(2)-OEt)(4)(HOEt)(2)(&mgr;(3)-O)(2)] (4), which represents another link in the chain of clusters produced by the reactions of 1 and simulating the build-up of polymeric molybdenum oxides by sol-gel methods. The crystal structure of 4 has been determined [C(12)H(32)Cl(4)Mo(4)O(12), triclinic, P&onemacr;, a = 7.376(2) ?, b = 8.807(3) ?, c = 11.467(4) ?, alpha = 109.61(1) degrees, beta = 92.12(3) degrees, gamma = 103.75(2) degrees, Z = 1]. By contrast, reaction of 1 with the nitrogen base NEt(3), followed by treatment with [PPN]Cl.2H(2)O ([PPN](+) = [Ph(3)P=N=PPh(3)](+)), gives the complex [PPN](+)[Et(3)NH](+)[Cl(2)(O)Mo(&mgr;(2)-O)(2)Mo(O)Cl(2)](2)(-) (6) in 90% yield. Its crystal structure [C(36)H(30)Cl(4)MoNOP(2), triclinic, Pna2(1), a = 21.470(6) ?, b = 16.765(2) ?, c = 9.6155(14) ?, alpha = 90 degrees, beta = 90 degrees, gamma = 90 degrees, Z = 16] includes the anion [Cl(2)(O)Mo(&mgr;(2)-O)(2)Mo(O)Cl(2)](2)(-), which is a charged derivative of the species forming the gels in sol-gel processes starting from chloromolybdenum ethoxides. Furthermore, compound 1 is found to be catalytically active in esterification and dehydration reactions of alcohols.     

CRYSTAL STRUCTDBE OF H_2(Et_4N)_2[Mo_8O_(26)]

<正> Mr= 1446.02, Monoclinic, P21/n, a = 11.841(2),b= 20.008(6), c= 12.053(8)A,β=105.15(3)°,V= 2756(3)A3,Z= 2, DC = 1.738 g·cm-3. Final R=0.035 for 4326 reflections. The title compound is the decomposition product of the trinuclear Mo cluster anion [Mo3(μ3-O)(μ-Cl)3(μ-OAc)3Cl3]-. The [No8O26]4- anion reported here has the a -type configuration, which consists of a ring made up of six edge-sharing [MoO5] octahedra linked loosely to two [MoO4] units.     

Research on Reactivities of MoCluster． A Selective Substitution Reaction of the Bridging（dtp） Ligand and Structure of Tetranuclear Molybdenum Cluster Compound ［Mo_4S_4（μ－O_2CC_6H_5）_2（dtp）_4］

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三核钼簇合物H[H2O]3[Mo3O(OAc)I3Cl6]的合成分子结构及红外光谱归属的研究

本文报道MoCl3.3H2O与乙酸作用生成三核钼簇合物H[H2O]3[Mo3O(OAc)3Cl6]的反应, 并用X射线单晶结构分析方法测定了簇合物的晶体结构, 结晶学参数. 结构分析结果表明该化合物阴离子为单氧帽等边三角形三核钼簇合阴离子, Mo-Mo平均距离2.569埃.对簇骼单元[Mo3O(μ-Cl)3Cl3]^2^+进行简正坐标分析. 从理论上对振动光谱谱带进行了归属. 10条IR谱带的观测和计算频率的平均偏差为1.15%. 本文讨论了特征谱带(包括金属键)的归属和力常数的合理性.     

Synthesis and structural characterization of the novel cluster compound

Reaction of [Mo3Y(mu-S)3(dtp)4(H2O)] (Y = O, S; dtp = S2P(OC2H5)2(-)) with HgI2 gave the novel compound [[Mo3S7(dtp)3]4 x I][(HgI3)3] x 4H2O (1), which contains a [[Mo3S7(dtp)3]4 x I] tetramer and (HgI3)-. Compound 1 has been characterized by IR, Raman, UV/Vis, and NMR spectroscopy and single-crystal X-ray diffraction analysis. It is shown that this formation process can be referred to as a new cluster reaction. The structure and spectroscopic data of the tetramer is also compared with that of the related discrete cluster [Mo3S7(dtp)3 x I]. Crystal data: space group F23, a = 26.786(3) A, V = 19218.7(4) A3, Z = 4, R = 0.059.