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.     

STUDIES ON SYNTHESES OF MoFe_3S_4 CUBANE-LIKE CLUSTER COMPOUNDS

The features of synthetic processes are described on the basis of the studies of the syntheses of MoFe_3S_4 cubane-like cluster compounds either by self-assembly reactions or by the conversion of linear clusters. The redox properties and the structure of ligands as well as the stoichiometry of reactants have obvious effects upon the core oxidation state and the structure of products. It is indicated that the self-assembly reaction may pass through a combination process oflinear cluster intermediates having structural unit (M,M'=Mo) Fe).     

Synthesis and Crystal Structure of S,S''''-Bis(8-quinolyl)-1,8-dithiaoctane

1INTRODUCTIONPreviously,wehavereportedsomeflexiblemultidentateligands,suchasO,O?bis(8-quinolyl)-1,8-dioxaoctane(ODOQ)[1],1,5-bis(8-quinolylsul-fanyl)-3-oxapentane(OESQ)and1,8-bis(8-quino-lylsulfanyl)-3,6-dioxaoctane(ODSQ)[2,3]formAgcomplexeswitheithersinglestranddouble-helicalstructuresordiscretecageskeletons.SimilarligandscontainingSatomsarelikelytoplayimportantrolesintheformationofdiscretecage-moleculesinwhichthefoldingeffectofsulfuratomsaffordsthebackboneofthespacerperpendicularto…     

双核钼铁硫簇合物[Fe(2, 2''-联吡啶3)][(S2MoS2FeCl2]的合成与晶体结构

双核Mo-Fe-S原子簇配合物[Fe(2,2′-bpy)₃][S₂MoS₂FeCl₂],是(Et₄N)₂MoS₄、FeCl₂和2,2′-联吡啶在乙腈中反应得到的结晶化合物.晶体属单斜晶系,空间群P2₁/c;a=9.328(3),b=26.788(2),c=13.764(3)Å;β=95.38(3)°;V=3424.2(11)ų;Z=4;D_c=1.698g/cm³;F(000)=1752.晶体结构用直按法解出;经全矩阵最小二乘法修正,最后R=0.068,R_ω=0.071(3933个I>3(σ)(I)的独立衍射).在晶体结构中配位阴离子[S₂MoS₂FeCl₂]^2-是排布在阳离子[Fe(2,2′-bpy)₃]²⁺所形成的空腔中.它是以非统计分布的形式存在,从而较准确地测定了各项键参数.Mo…Fe距离为2.773(2)Å,Mo-S_b和Fe-S_b有大致相等的键长.     

四核钴簇合物[Co_4(mp)_5(PBu_3~n)_3]的快原子轰击质谱碎片和结构的相互关联

本文通过实验,选择质量1463u、含有四个钴原子具有三种不同配位环境的标题簇合物为研究对象,以快原子轰击软电离方法,探讨质谱碎片与簇合物结构间的相互关联。     

氮杂芳基三脚架配体及其金属超分子化合物

氮杂芳基三脚架配体可分为柔性和刚性两种，它们均有三个或三个以上的配位点，配体中配位点数目和位置的改变都会对金属超分子配合物的结构产生很大的影响。本文简单介绍了氮杂芳基三脚架配体自组装的特点及其所生成的超分子化合物的主要结构类型。     

新奇的Mo/Fe/S原子簇的合成及[Me_3PhCH_2N]_2[MoFe_4S_4(SC_6H_(11))_7]的结构表征

在 (NH4) 2 MoS4,FeCl2 ,NaSC6 H1 1 (C6 H1 1 为环己基 )的甲醇反应体系中得到一种新型的 [Me3PhCH2 N] 2 [MoFe4S4(SC6 H1 1 ) 7]的钼铁硫立方烷原子簇 ,并进行了结构表征 .它的晶体属三斜晶系 ,空间群P 1,a =1.5 2 3 1( 3 )nm ,b =1.610 5 ( 3 )nm ,c=1.83 83 ( 4 )nm ,α =77.18( 3 )° ,β =75 .17( 3 )° ,γ =64 .60 ( 3 )° ,Z =2 .讨论了由于环烷巯基参与而引起的反应产物及其结构变化     

过渡金属配合物的结构规律及Fe_3(bdt)_3(PBu_3~n)_3的合成与结构

本文总结邻苯二硫酚(H_2bdt)在一系列过渡金属化合物中的结构规律,并报道在三丁基膦作用下簇合物Fe+3(bdt)_3(Pbu_3~n)_3,的生成反应。化合物属三斜晶体的P空间群,单胞参数:a=13.283(3),b=20.115(5),c=13.156(3),α=90.33(2),β=116.47(1),γ=92.19(2)°,Z=2,d_c=1.26g/cm~3;结构以直接法解出,以I>4σ(I)的4122个独立衍射点进行计算,最终收敛至R(R_w)=0.053(0.060)。化合物有较强的顺磁性。     

折叠型双银配合物电子结构与相关性质

在密度泛函B3LYP/LanL2DZ的水平上,对具有π-π弱相互作用调控的折叠型银配合物Ag₂(MPTQ)₂²⁺进行计算研究。探讨该配合物的电子结构、成键特征、π-π弱相互作用机理、电荷布居及其相关性质。计算结果表明,Ag…Ag之间存在弱的直接相互作用,HOMO主要布居在配体中芳香环的σ-p轨道、S的σ-p轨道及与S相连的C12的S轨道上,LUMO主要布居在配体中芳香环的π^*-p轨道上,基态电子光谱主要是配体中的n→π^*跃迁产生的电荷转移光谱。论文还讨论了分子间π-π弱相互作用的本质及活性部位等。计算结果能较好地解释实验现象与规律。