钼铁硫簇合物催化乙炔还原活性及其与组成和结构的关系

在25℃和无氧条件下,以KBH_4为还原剂,测定了七种Mo-Fe-S簇合物(Ⅰ.(Et_4N)_4 [Mo_2Fe_2S_(10)]·2CH_3OH,Ⅱ.Mo_2Fe_2S_4(S_2CNEt(?))_5·CH_3CN,Ⅲ.(Bu_4N)_3[Mo_2FeS_3O],Ⅳ.(Et_4N)_3[Mo_2FeS_3O_2],Ⅴ.(Et_4N)_2[MoFeS_4(SCN)_2(OCH_3)_2]·3CH_3OH,Ⅵ.(Et_4N)_3 [Mo_2FeS_3O(OCH_3＇2],Ⅶ.(Et_4N)_4[Mo_2Fe_7S_(12)(SPh)_6]·6CH_3OH),三种Fe-S簇合物(Ⅷ.(Et_4N)_4[Fe_4S_4(S_2CNEt_2＇4],Ⅸ.(Bu_4N)_2[Fe_4S_4(SC(CH_3) 3)4],Ⅹ.(Bu_4N)[Fe_2S_3(SCH_2Ph)_2])和相关化合物的组合体系的催化乙炔还原活性.还在15℃和其它条件不变的情况下,测定了九种(?)由(NH_4)_2MoS_4和FeCl_3组成的不同组分的组合体系的催化乙炔还原活性.对上述实验结果进行了讨论.     

钼铁硫簇合物的合成、结构和性质研究

本文综合报导[(C_4H_9)_4N]_3[Fe(MoS_4)_2O],[(C_2H_5)_4N]_3[Fe(MoS_4)_2O_2],[(C_2H_5)_4N]_3 [Fe(MoS_4)_2O_2]·CH_3CH,[(C_4H_9)_4M]_2[Mo_2S_6O_2],[(C_2H_5)_4N]_3{[(SCH_2CH_2S)MoS_3]_2Fe}和[(C_2H_5)_4N]_4[Fe_6S_9(SCH_2CH_2OH)Cl]六种簇合物的合成、结构和性质研究。在Nicolct R_3 system四园单晶衍射仪上,用CuK_a(MoK_a)辐射收集数据,用SHELXTL程序,重原子法解出这些簇合物的晶体结构。用红外光谱,紫外可见光谱和穆斯堡尔谱对簇合物进行了物理性质的测定。同时在还原剂KBH_4存在下,对簇合物的催化乙炔还原为乙烯的活性也进行了测定。并结合量子化学计算探讨了簇合物的电子结构和性能之间的关系。     

A STUDY ON THE ACTIVITY OF Mo-Fe-S CLUSTER COMPOUNDS FOR CATALYTIC REDUCTION OF C_2H_2 AND ITS RELATION TO THE COMPOSITION AND STRUCTURE OF SUCH COMPOUNDS

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.     

[Et_4N]_3[Mo_2FeS_8O_2]·CH_3CN原子簇络合物的合成、性质和结构

本文研究了一种新的钼原子含端氧配位的Mo-Fe-S原子簇络合物[Et_4N]_3·[Mo_2FeS_8O_2]·CH_3CN(Ⅰ)的合成、性质和结构,与[Et_4N]_3[Mo_2FeS_8O-2](Ⅱ)和[Bu_4N]_3[Mo_2FeS_8O](Ⅲ)对比得出:(1) 三种络合物得电子能力的顺序为:Ⅰ<Ⅱ<Ⅲ.(2)它们在空气中的稳定性顺序为:Ⅰ>Ⅱ>Ⅲ.(3)它们的分子对称性强弱的顺序为:Ⅱ>Ⅰ>Ⅲ.(4)催化乙炔还原为乙烯的活性顺序与它们的稳定性正相反.     

两种单齿硫醇为配位体的钼络合物的合成和结构表征

本文报导利用MoC1_5、NaOMe、C_6H_5CH_2SH和NaHS在无氧、无水,室温条件下在甲醇介质中合成(Et_4N)_2[Mo_2O_2S_2(SCH_2C_6H_5)_4](化合物Ⅰ)和(Et_4N)-[Mo_2O_2(μ-SCH_2C_6H_5)_3(SCH_2C_6H_5)_4](化合物Ⅱ)的反应条件,分离步骤。本文同时报导这两种化合物的核磁共振谱、红外光谱、电子光谱等结构表征,同时也对化合物形成的可能机理作了探索性的讨论。     

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。     

四钼簇合物Mo_4(μ_3—O)_2O_4Cl_2(OCOC_6H_5)_6和[Mo_4(μ_3—O)_2O_4Cl_2(OCOC_6H_4CH_3)_6]·2C_6H_5Cl的合成、结构、反应机理及光谱性质研究

用MoCl_5和C_ 6H_5COOH(或CH_3C6H_4COOH)在氯苯溶液中反应,得到四钼簇合物Mo_4(μ_3-O)_2O_4Cl_2-(OCOC_6H_5)_6(或[Mo_4(μ_3-O)_2O_4Cl_2(OCOC_6H_4CH_3)_6]·2C_6H_5Cl)晶体。用X射线单晶衍射法测定了簇合物的晶体结构,运用18电子规则及簇合物的晶体结构数据,得到金属Mo-Mo键键价为1,钼在簇合物中均呈+5价。进行了反应机理的探讨,簇合物中端基氧和桥基氧的存在来自于苯甲酸(对甲基苯甲酸),MoCl_5和C_6H_5COOH(CH_3C_6H_4COOH)作用时,首先生成钼的含氧配合物MoOCl_3,然后生成双核钼配合物Mo_2(μ_2-O)_2O_2Cl_2,进一步形成配合物。红外光谱、激光拉曼光谱和磁化率的测定证明了结构分析的结果。值得注意的是,固体表面光电压谱和固体光声光谱的测定,簇合物Mo_4(μ_3-O)_2O_4Cl_2(OCOC_6H_5)_6的表面光电压谱在～600nm处有一光致电荷分离谱带。     

原子簇配合物〔(C_4H_9)_4N〕_2〔Mo_2S_6O_2〕的合成、结构和性质研究

用(NH_4)_2MoS_4、FeCl_3和(C_4H_9)_4NBr在CH_3OH-CH_3ONa溶液中反应,得到了原子簇配合物[(C_4H_9)_4N]_2[Mo_2S_6O_2]晶体,用X-射线单晶衍射方法测定了簇合物的晶体结构,晶体属空间群D_(2h)~(15)-P_(c a h),晶胞参数为a=15.876(3),6=17.786(6),c=31.90(1),V=9008.7~3,经块矩阵最小二乘法修正,最终得偏离因子R=0.0659,同时对簇合物的红外光谱、拉曼光谱、紫外可见光谱以及电化学性质也进行了研究。     

若干含氧桥双核钼(Ⅴ)原子簇化合物的研究

本文在测定了五个新颖双核钼(Ⅴ)簇合物的晶体结构(QH)_4[Mo_2O_4(NCS)_6](1),H(PyH)_3·[Mo_2O_4(C_2O_4)_2(H_2O)_2]_2·2H_2O(2),(QH)_3[Mo_2O_4(C_4H_3OCOO)(NCS)_4](3),(QH)_3[Mo_2O_4·(CH_3OH)(NCS)_5](4)和(PyH)_4[Mo_2O_3(SO_4)(NCS)_6](5)以及文献报道该类型化合物结构数据的基础上,综述了含氧桥双核钼(Ⅴ)簇合物的结构特征,并应用SCC-EHMO方法探讨了该类型化合物的电子结构和成簇机理,最后用简正坐标分析法,研究了含氧桥双核钼(Ⅴ)化合物簇胳单元[Mo_2O_4]~(2 )和[Mo_2O_3SO_4]~(2 )的振动结构及其红外谱带归属。     

低价双核Mo—S—CO簇合物的质谱研究

本文报道了二个低价钼簇合物的快原子轰击(FAB)和电子轰击(EI)质谱:(Et_4N)_2[Mo_2(CO)_8(μ-SPh)_2]的FAB和FAB—NI谱及Mo_2(CO)_8(μ-SPh)_2的FAB和EI谱。分别获得它们的完整的配位阳离子和阴离子峰。这类簇合物的大致裂断解途径可能是首先脱CO、然后脱C_6H_5—,在EI—MS谱中观察到双金属离子裂解为单金属碎片离子的反应。文中探讨了质谱条件下标题簇合物的氧化还原反应。研究结果同时表明,Mo价态明显影响碎片离子峰的相对丰度和Mo对配位体CO、—SPh、—S的络合能力。另外,还报道了Mo_2(CO)_6(μ-SPh)_2(CH_3CN)_2的FAB—MS和EIMS谱。     

NEW RING SYSTEMS OF ELEMENTS OF MAIN GROUPS IV AND V

Abstract

The synthesis of [PhSn(O)O₂CC₆H₁₁]₆ represents the first example of tin(IV) in a drum-shaped molecule. The formation of the dimeric composition, [(MeSn(O)O₂CC₆H₁₁)₂(MeSn(O₂CC₆H₁₁)₃]₂, appears to be an intermediate hydrolysis product on the way to the drum composition. The X-ray structure reveals an “unfolded” drum array. The distannoxane unit which is represented as the sides of the drum is found in additional new dimeric compositions, [(SCH₂CH₂O)₂SnCl]₂[H][Et₄N], [((CN)₂C₂S₂)₂SnOH]₂, and [BuSnCl₂(OH) · H₂O]₂. These all have six-coordinated tin atoms which contrasts to the dimeric aryl distannoxanes recently isolated, [Ph₂(Cl)SnOSnPh₂(X)]₂, X = OH, Cl, containing five-coordinated tin. Also isolated are the new ring containing, five-coordinated tin derivatives, [(SCH₂CH₂S)₂Sn]₂[SCH₂CH₂S][Et₃NH]₂ and [(SC(CN)C(CN)S)₂SnMe][Et₄N]. The former has two trigonal bipyramidal tin atoms while the latter composition has a square pyramidal geometry. Related ring systems of new five-coordinated derivatives of silicon, germanium, arsenic, and antimony that span the range between the two ideal five-coordinated geometries also have been structurally characterized.     

Ligand substitution in the cluster complex [Mo3S7Cl6]2?: Synthesis and crystal structure of (Et4N)[Mo3S7Cl5(CH3CN)]

The crystal structure of the new cluster complex (Et₄N)₂[Mo₃S₇Cl₆] · CH₃CN · H₂O (I) was determined. Heating of a solution of I in CH₃CN under solvothermal conditions (120°C) induces replacement of one Cl⁻ ligand by CH₃CN to give (Et₄N)[Mo₃S₇Cl₅(CH₃CN)] (II). The product was also studied by X-ray diffraction analysis.     

SYNTHESIS AND CHARACTERIZATION OF TWO NOVEL,NEST-SHAPED Mo-Cu-S CLUSTER COMPOUNDS, [MoOS3Cu3(Py)5X] (X = Br,I), AND THE SUBSTITUTION OF Mo-Cu-S CLUSTERS

Abstract

The title compounds [MoOS₃Cu₃(Py)₅Br] (3) and [MoOS₃Cu₃(Py)₅I] (4) were obtained through the nest-shaped cluster [(n-Bu)₄N]₂[MoOS₃Cu₃BrCl₂] (1) and twin-nest-shaped cluster [Et₄N]₄[Mo₂Cu₆S₆O₂Br₂I₄](2) by reacting with pyridine. They show nest-shaped skeletons, and are characterized structurally by single-crystal X-ray analysis. These are the first neutral nest-shaped Mo(W)-Cu(Ag)-S clusters.     

Studies,on the synthesis,structure, IR spectra and reactivity of a new dinuclear Mo(0) complex, [Et4N]2[Mo2(CO)8(SCH2CO2Et)2]

Reaction of Et₄NI, NaSCH₂CO₂Et and Mo(CO)₆ in CH₃CN affords a new dinuclear molybdenum (0) complex, [Et₄N]₂[Mo₂(CO)₈(SCH₂CO₂Et)₂] (1). Electrochemistry and reactivity investigation indicate that 1 undergoes an interesting two-electron oxidation in a single step (-0.43 V) and a substitution of its carbonyls by coordinating solvents resulting in two kinds of Mo(I)-complexes, Mo₂(CO)₈(SCH₂CO₂Et)₂ and (Mo₂(CO)₆SCH₂CO₂Et)₂(CH₃CN)₂. vC=O and vMo-CO have been assigned. The crystal and molecular structure has been determined from three-dimensional X-ray data. 1 crystallized in the triclinic, space group with a=10.362(1), b=10.391(1), c= 10.815(2)Å; α=91.64(2)°, β=100.07(2)°, γ=114.46(1)°; Z=1; R=4.8% for 2975 reflections with I>3σ(I). Nonbonding of Mo … Mo [3.939(1)Å] and the configuration of MoS₂Mo unit in 1 are very different from those in related Mo(I)-product. These results confirm our previous speculation that the two-electron character derives from creation or cleavage of a metal-metal single bond coupled with structural rearrangement in a bridged bimetallic center.     

Mobybdenum(VI)-oxygen complex containing citrage ligand: synthesis and characterization of K6[Mo2O5(cit)2]·5H2O

The complex, K₆[Mo₂O₅(cit)₂]·5H₂O was obtained by crystallization from reaction of [Et₄N]₃[Mo₂FeS₈O₂ and potassium citrate (K₃cit) in methanol and water under an atmosphere of pure nitrogen at ambient temperature. The complex is triclinic, space group P1, a = 11.843(8) Å, b = 13.717(8) Å, c = 10.287(5) Å, α = 108.11(4) °, β = 99.42(5) (1) °, γ = 66.52(4) °, R = 0.034 for 4510 observed (I > 3 σ (I)) reflections. Single crystal structure analysis reveals that citrate ligand coordinated to molybdenum atom through two carboxylato oxygens and one deprotonated hydroxyl oxygen together with one bridging oxygen atom and two terminal oxygen atoms completes distorted coordination octahedron around each molybdenum atom. IR spectra are in agreement with the structure.     

Selenium-capped trimolybdenum and tritungsten carbonyl clusters [Se2M3(CO)10] (M = Mo, W)

A facile synthesis of the novel selenium-capped trimolybdenum and tritungsten ring carbonyl clusters [Se₂M₃(CO)₁₀]²⁻ (M = Mo, 1; W, 4) have been achieved. The selenium-capped trimolybdenum cluster compound [Et₄N]₂[Se₂Mo₃(CO)₁₀] ([Et₄N]₂[1]) can be obtained from the reaction of the trichromium cluster compound [Et₄N]₂[Se₂Cr₃(CO)₁₀] with 4 equiv. of Mo(CO)₆ in refluxing acetone. On the other hand, when [Et₄N]₂[Se₂Cr₃(CO)₁₀] reacted with 4 equiv. of W(CO)₆ in refluxing acetone, the planar cluster compound [Et₄N]₂[Se₂W₄(CO)₁₈] ([Et₄N]₂[3]) was isolated, which could further transform to the tritungsten cluster compound [Et₄N]₂[Se₂W₃(CO)₁₀] ([Et₄N]₂[4]) in good yield. Alternatively, clusters 1 and 4 could be formed from the reactions of the monosubstituted products [Et₄N]₂[Se₂Cr₂M(CO)₁₀] (M = Mo; W, [Et₄N]₂[2]) with 3 equiv. of M(CO)₆ in acetone, respectively. Complexes 1-4 are fully characterized by IR, ⁷⁷Se NMR spectroscopy, and single-crystal X-ray analysis. Clusters 1, 2, and 4 are isostructural and each display a trigonal bipyramidal structure with a homometallic M₃ ring (M = Mo, 1; W, 4) or a heterometallic Cr₂W ring that is further capped above and below by μ₃-Se atoms. Further, the intermediate planar complex 3 exhibits a Se₂W₂ square with each Se atom externally coordinated to one W(CO)₅ group. This paper describes a systematic route to a series of selenium-capped trimetallic carbonyl clusters and the formation and the structural features of the resultant clusters are discussed.     

Synthesis of [MoOS3Cu3I(3, 5-diMePy)4]·CH3CN and (Et4>N)4[Mo4Cu8O4S12{(Ph2PS)2N}4] from Solid State Product [Et<

Treatment of iodide bridged dimer [NEt₄]₄[Mo₂O₂S₆Cu₆I₄Br₂] 1 with 3,5-bimethylpyridine or with Kin CH₃CN afforded the tetranuclear cluster [MoOS₃Cu₃I(3,5-diMePy)₄]·CH₃CN 2 and dodecanuclear cluster (Et₄N)₄[Mo₄Cu₈O₄S₁₂{(Ph₂PS)₂N}₄] 3. Monomeric 2 possess a nest shaped skeleton. The structure of oligomeric 3 can be regarded as a tetramer of nest shaped MoCu₃OS₃ groups co polymerized by sharing the limbic Cu atoms.     

Mechanochemical Synthesis of Tri-μ2-Disulfido-μ3-Thio-Tris(Diethyldithiocarbamato)-S,S"-triangular- Trimolybdenum Diethyldithiocarbamate {Mo3(μ3-S)(μ2-S2)3[(C2H5)2NCS2]3}+[(C2H5)2NCS2]–

The mechanoactivated solid-state reaction of [Et₄N]₂[Mo₃S₇Br₆] with Na(Et₂NCS₂) in a vacuum vibration ball mill yields the [Mo₃S₇(Et₂NCS₂)₃]⁺[Et₂NCS₂]^–complex. The product was studied by IR and Raman spectroscopy and differential thermal analysis.     

Localized molecular orbital study on chemical bonding and reactivities of certain Mo-Cu-S cluster compounds

The localized molecular orbitals (LMOs) and Mulliken bond orders for the cluster anions of [Et₄N]₂[Mo₂S₄(edt)₂] (1), [(CH₃CH₂)₄N][Mo₂CuS₄(PPh₃)(edt)₂] (2) and the cluster molecule [Mo₂Cu₂S₄(PPh₃)₂(edt)₂] (3) have been calculated by means of the Edmiston-Ruedenberg energy localization technique under the CNDO/2 approximation. The results of the LMOs calculations show that there are two pairs of (S₁ Mo) bonds each pair of the Mo atoms and the terminal S₁ atoms in the anion of (1). In the addition reactions of the cluster compound (1) with one or two Cu atoms these (S₁ Mo) bonds are sequentially opened and form correspondently the cluster compounds (2) and (3) with the three-centered or four-centered bonds among the copper, sulfur, and molybdenum atoms, accounting for the stronger bonding of the Cu atom to the Mo-S cluster compounds such as (1). This also gives the explanation of chemical bonding for the [2+1] and [2+2x1] synthetic reaction schemes of the compounds (2) and (3). The structural features for the cluster compounds studies are briefly discussed as well.     

Beiträge zur Koordinationschemie von Rhenium(III)chlorid in nichtwäßrigen Lösungen

Coordination reactions of solutions of Re₃Cl₉ in acetonitrile, propanediol-1,2-carbonate, acetone and dimethylsulfoxide yield compounds with unchanged metal-cluster structures. The following compounds were isolated and characterised: [Et ₄N]₃[Re₃Cl₉(N₃)₃], [Et ₄N]₃[Re₃Cl₆(N₃)₆], [Et ₄N]₃[Re₃Cl₃(N₃)₉], [Et ₄N]₃[Re₃Cl₉(CN)₃], [Et ₄N]₃[Re₃Cl₃(CN)₉],Et ₄N]₃[Re₃Cl₉(NCS)₃], [Et ₄N]₃[Re₃Cl₆(NCS)₆], [Et ₄N]₃[Re₃Cl₃(NCS)₉], Re₃Cl₉·(DMSO)₃, Re₃Cl₉·(HMPT)₃.