具有含磷、硫配体的二核和三核钌羰基簇合衍生物的合成及晶体结构

用Ru₃(CO)12与杂环二硫代次膦酸盐SP(C₆H₄OR)(S)N(C₆H₅)NC(Me)(R=Me,Et)反应,得到两类4个含磷、硫配体的二核和三核钌羰基簇合衍生物Ru₃(CO)₈(μ₃-S)₂[P(C₆H₄OR)N(C₆H₅)NC(Me)S](1;R=Me;3;R=Et)和Ru₂(CO)₆[μ-η₂-SC(Me)NN(C₆H₅)P(C₆H₄OR)](2;R=Me;4;R=Et).对它们进行了元素分析、IR、¹HNMR和MS谱学表征,并用X射线衍射技术测定了1和2的晶体结构.晶体1属三斜晶系,P1空间群,晶胞参数a=1.0755(2)nm,b=1.5760(2)nm,c=0.9078(1)nm,α=98.12(7)°,β=96.64(4)°,γ=79.67(5)°,V=1.4921(4)nm³,Z=2,R(wR)=0.0303(0.0615);该簇合物分子为开口三核钌簇,其簇骨架Ru₃(μ₃-S)₂为畸变四方锥构型;五元杂环上的P原子取代在Ru1原子的轴向配位位置上.晶体2属单斜晶系,P2(1)/n空间群,晶胞参数a=1.1243(4)nm,b=1.4105(5)nm,c=1.62945(7)nm,β=107.06(5)°,V=2.4702(2)nm³,Z=4,R(wR)=0.0248(0.0441);两核簇合物分子中含有2个六元螯环Ru1SCNNP和Ru2SCNNP,增强了簇合物的稳定性.

Synthesis and Crystal Structure of Dinuclear and Trinuclear Ruthenium Carbonyl Clusters with P, S-Contained Ligand

The reactions of carbonyl ruthenium Ru3(CO)12 with two cyclic dithiophosphinate SP(C6H4OR)(S)N(C6H5)N C(Me)(R=Me, Et) yields four novel dinuclear and trinuclear ruthenium carbonyl clusters with P, S-containing lignads Ru3(CO)8(μ3-S)2 [ P (C6H4OR)N(C6H5)NC(Me)S](1; R=Me; 3; R=Et) and Ru2(CO)6 [μ-η2-P(C6H4OR)N(C6H5)NC(Me)S](2; R=Me; 4; R=Et). These clusters were characterized by elementary analysis, IR, 1H NMR and MS spectroscopy. The crystal structures of clusters 1 and 2 were determined by X-ray diffraction techniques. The crystal of cluster 1 belongs to triclinic system with space group P1, a=1.075 5(2) nm, b=1.576 0(2) nm, c=0.907 8(1) nm, α= 98.12(7)°, β=96.64(4)°, γ=79.67(5)°, V=1.492 1(4) nm3, Z=2, R(wR)=0.030 3(0.061 5). The molecule consists of a opened triangle of ruthenium atoms capped above and below the plane by sulphur. Ru3(μ3-S)2 core is a distorted square pyramid geometry. The site of five-membered hetero cyclic phosphine substitution is equatorial to the tri-ruthenium plane and is at an axial site of Ru1. The crystal of cluster 2 belongs to monoclinic system with space group P2(1)/n, a= 1.124 3(4) nm, b=1.410 5(5) nm, c=1.629 45(7) nm, β=107.06(5)°, V=2.470 2(2) nm3, Z=4, R(wR)=0.024 8(0.044 1). The dinuclear cluster contains two six-membered chelate rings Ru1SCNNP and Ru2SCNNP, they enhance the stability of the cluster.