含硫磷桥基的两核铁羰基簇合物的合成和晶体结构  

Synthesis and Crystal Structure of D inuclear Iron Carbonyl Clusters Containing a Phosphido-Thiolato Bridging Ligand

作　　者：宫培军[1] 吴秉芳[1] 胡其图[1] 刘树堂[1] 

机构地区：[1]内蒙古大学化学化工学院,呼和浩特010021

出　　处：《无机化学学报》2001年第6期794-798,共5页Chinese Journal of Inorganic Chemistry

基　　金：国家自然科学基金资助项目(No.29861001);内蒙古自然科学基金资助项目No.980201

摘　　要：Fe3CO12与杂环二硫代次膦酸盐SPC6H4ORSNC6H5NCMeR=MeEt反应得到两个新的含硫磷桥基的双核铁羰基簇合物Fe2CO6μη2SCMeNNC6H5PC6H4OMe和Fe2CO6μη2SCMeNNC6H5PC6H4OEt以及簇合物Fe3CO9μ3S2已知。对它们进行了元素分析IR1HNMR和MS等谱学表征并用Xray衍射技术测定了的晶体结构。该晶体属单斜晶系P21/n空间群晶胞参数a=11.1922b=14.2723c=16.2813β=108.223°V=2470.283Z=4。两核簇合物中含有两个桥基FeSFe和FePFe而且C7N2N1链连结在S、P原子间形成了两个六员螯环Fe1SCNNP和Fe2PNNCS增强了簇合物的稳定性。The reaction of Fe3(CO)12with two cyclic dithiophosphinate S P(S)(C6H4OR)N(C6H5)NC(Me )(R =Me,Et ),yields two novel dinuclear iron carbonyl clusters contining a phosphi do-thiolato bridgingμ-η2-SCNNP ligand Fe2(CO)6[μ η2-SC(Me )NN(C6 H5)P(C6H4 OMe )]?,Fe2(CO)6[μ η2-SC(Me)NN(C6H5)P(C6H4 OEt )]?and cluster Fe3(CO)9(μ3-S)2(known).We suggest that during the reaction ,the ligand precursor has been cleaved in its P =S and P-S bonds and opened its ring to give the fragments as ligandsμ3-S,μ-η2-SC(Me )NN(C6H5)P(C6H4OR)that coordinated to the iron atoms of the decarbonyl fragmental Fe3(CO)12to form the clusters as listed above.The clusters were characterized by elemental analysis,IR,1H NMR and Ms spectrometric methods ,and the molecular structure of cluster?has been determined by X-ray diffrac tion method,it belongs to monoclini c with space group P2(1)/n,a=11.192(2)?,b=14.272(3)?,c=16.281(3)?,V=2470.2(8)?3,β=108.22(3)°,Dc=1.565g·cm-3,Z =4,F(000)=1176,R=0.0460,R w=0.1196.The din-uclear cluster has two bridges Fe-S-Fe and Fe-P-Fe,and the chain C (7)-N(2)-N(1)link the sul-phur atom and the phosphorus atom ,th at contains two six-membered chelate rings Fe(1)SCNNP and Fe(2)PNNCS in the cluster,they enhanced t he stability of the cluster.

关 键 词：双核铁羰基簇合物 硫磷桥基配体 合成 晶体结构 

分 类 号：O614.811[理学—无机化学]