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  

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

作　　者：韩瑞敏[1] 吴秉芳[1] 胡襄[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：《高等学校化学学报》2004年第2期216-220,共5页Chemical Journal of Chinese Universities

基　　金：国家自然科学基金 (批准号 :2 98610 0 1);内蒙古自治区教育厅科学基金 (批准号 :ZD0 10 71)资助

摘　　要：用 Ru3( CO) 1 2 与杂环二硫代次膦酸盐 SP( C6 H4 OR) ( S) N( C6 H5) 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( C6 H4 OR) N( C6 H5) NC( Me) S]( 1 :R=Me;3 :R=Et)和 Ru2 ( CO) 6 [μ-η2 -SC( Me) NN( C6 H5) P( C6 H4 OR) ]( 2 :R=Me;4:R=Et) .对它们进行了元素分析、IR、 1 H NMR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 .0 75 5 ( 2 ) nm,b=1 .5 760 ( 2 ) nm,c=0 .90 78( 1 ) nm,α=98.1 2 ( 7)°,β=96.64( 4 )°,γ=79.67( 5 )°,V=1 .492 1 ( 4 ) nm3,Z=2 ,R( w R) =0 .0 3 0 3 ( 0 .0 61 5 ) ;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 .1 2 43 ( 4 ) nm,b=1 .41 0 5 ( 5 ) nm,c=1 .62 945 ( 7) nm,β=1 0 7.0 6( 5 )°,V=2 .470 2 ( 2 ) nm3,Z=4,R( w R) =0 .0 2 48( 0 .0 441 ) ;两核簇合物分子中含有 2个六元螯环Ru1 SCNNP和 Ru2 SCNNP。The reactions of carbonyl ruthenium Ru_3(CO)_ 12 with two cyclic dithiophosphinate SP(C_6H_4OR)(S)N(C_6H_5)N C(Me)(R=Me, Et) yields four novel dinuclear and trinuclear ruthenium carbonyl clusters with P, S-containing lignads Ru_3(CO)_8(μ_3-S)_2 [ P (C_6H_4OR)N(C_6H_5)NC(Me)S](1: R=Me; 3: R=Et) and Ru_2(CO)_6 [μ-η 2-P(C_6H_4OR)N(C_6H_5)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) nm 3, 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. Ru_3(μ_3-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) nm 3, 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.

关 键 词：二核钌羰基簇合衍生物 三核钌羰基簇合衍生物 含硫配体 含磷配体 合成 晶体结构 

分 类 号：O614.821[理学—无机化学] O641.4[理学—化学]