钼铁硫原子簇化合物的合成与结构化学——Ⅳ.双类立方烷化合物与酰氯的反应

我们曾利用类金刚烷结构的多铁巯基化合物(Et_4N)_2[Fe_4(SR)_(10)](R为拉电子的芳基C_6H_5或C_6H_4CH_3)与(Et_4N)_2MoS_4的反应,合成了一系列含有Fe(SR)_6桥的双类立方烷化合物[{Mo(FeL)_3S_4}_2(μ_2-SR)_6Fe]~(z-)(L=SR,z=4;R=Ph,1a;R=o-C_6H_4CH_3,1d;R=m-C_6H_4CH_3,1e;R=p-C_6H_4CH_3,1f)。测定了它们的单晶结构,并开展了磁学研究。确认它们都具有1的阴离子结构,其Mo-Fe-Mo’距离都在7.2A左右。当R为推电子的脂肪族基因(如Et或CH_2C_6H_5)时,其相应的距离为6.6—6.7A。原子距离的数据提示,我们     

铁钼硫原子簇化合物的合成与结构研究 Ⅴ.[MoFe_3S_4]类立方烷簇合物的转化反应和[Et_4N]_3[Mo_2Fe_6S_8(SC_6H_4CH_(3-m))_3Cl_6]的晶体结构

具[MoFe_3S_4]类立方烷结构单元的双类立方烷化合物[Et_4N]_4[Mo_2Fe_7S_8(SR)_(12)](1a,R=Ph;1b,R=tolyl-m)或单类立方烷化合物[MoFe_3S_4(dtcR_2)_5](2a,R=Me;2b,R=Et)与酰氯在乙腈中反应,分别得到不含Fe桥的双类立方烷化合物(Et_4N)_3[Mo_2Fe_6S_8(SR)_3Cl_6](3a,R=Ph;3b,R=tolyl-m)与[MoFe_3S_4]骨架支解后的Fe(dtcR_2)_2Cl(4a,R=Me;4b,R=Et)。说明在相同反应条件下,[MoFe_3S_4]单元在1中比在2中稳定。本文首次将1型与3型结构通过一步化学反应连系起来。3型化合物的产生得到X射线衍射测定及~1H NMR谱的证实。本文报道3b的单晶结构及3的~1H NMR数据。3b属六方晶系,P6_3/m,a=1.6827(3),c=1.5951(16)nm;V=3.91158nm~3;D_c=1.491g/cm~3;Z=2;F(000)=1780;偏离因子R=0.048。化合物2与酰氯反应产生4,由红外及紫外可见光谱证实。     

银配合物[Ag(OPOQ)](BF_4)(OPOQ=O,O''''-双(8-喹啉基)-1,3二氧丙烷)的合成与表征

四氟硼酸银和配体O,O＇-双（8-喹淋基）-1,3-二氧丙烷（OPOQ）反应,生成标题配合物[Ag（OPOQ）]（BF4）（C21H18AgBF4N2O2,Mr=525.05）,并通过了元素分析、红外光谱、核磁氢谱及X-单晶结构表征。配合物的晶体为单斜晶系,空间群为P21/n,晶胞参数a=12.009（6）,b=14.594（7）,c=12.124（6）A;β=111.875（8）°,V=1972.0（17）A3,Dc=1.769g/cm3,Z=4,μ（MoKα）=1.081mm-1,F（000）=1048,S=1.066。最终偏离因子R=0.0336,wR=0.0414。晶体结构显示,该配合物的阳离子是一个半包围的弓形结构。     

Diphosphine mediated assembly of multinuclear silver complexes containing the thiolato ligand 2-mercaptobenzoxazole(Hmbo)

A new complex [Ag4-S-mbo)4(dppp)4](1) is obtained from the reaction of AgBF4 and Hmbo(2-mercaptobenzoxazole) with the participation of dppp(bis(diphenylphosphino) propane). Single crystal X-ray diffraction analysis shows that it is discrete neutral molecule and composed of two asymmetrical moieties. Four Ag atoms in each molecule are completely coplanar and of similar environment. The ligands Hmbo and dppp in complex 1 bridge two Ag atoms through "μ2-S-mbo" and P atoms in two ends, respectively. The possible mechanism of the reaction is provided, and the sequence of adding materials and the length of backbone (CH2)n in diphosphine play an important role in the results of the reactions.     

簇合物Co6S8(PBun3)6的晶体结构及簇骼M6E8P6(E=S,Se,Te)的协同效应

簇骼为M6E8P6的六核簇合物的一个新成员--Co6S8(PBun3)6的合成和晶体结构表明,可能是由3个单核基元Co(PBun3)2S先组装成三核簇状基元化合物Co3(μ2-S)3(μ3-S)(PBun3)3,然后由2个这样的三核亚单元形成μ3-S桥生成该六核簇合物.讨论了簇骼为[M6E8P6]n(M=Fe,Mo,Co,Cr,W;E=S,Se,Te;n=-1,0,+1,+2,+3)的系列簇合物的分子内协同效应.     

铁钼硫原子簇化合物的合成与结构研究I.(Et~4N)~4IMo~2Fe~7S~8(SPh)~12]的合成与晶体结构

本文通过对巯基铁与MoS~4^2-反应的研究,对双立方烷型铁-钼-硫原子簇化合物的形成途径及中间物作了讨论.同时报道了[Fe~4(SPh)~10](Et~4N)~2K与[MoS~4][Et~4N]~2反应的产物(Et~4N)~4-[Mo~2Fe~7S~8(SPh)~12(2)的合成,晶体结构,红外光谱和磁化率.晶体2属三斜晶系,Mr=2670.3;空间群PI;a=12.775(4),b=13.076(3),c=20.576(4)A;α=80.00(2),β=81.39(2),γ=61,51(2);V=2966.3(14)A~3;Z=1;Dc=1.495g.cm^-3;F(000)=1378;偏离因子R=0.077.特别指出了分子中Mo-Mo'的距离[7.188(6)A]是当今同类化合物中最长的,它对研究固氮酶活性中心模型物的合成和结构规律,有重要意义.     

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…