含面桥基磷硫配体的新颖三核和四核钌羰合簇  

Synthesis and Structure of Novel Trinuclear and Tetranuclear Ruthenium Carbonyl Clusters Containing μ_3-P orμ_3-PR and μ_3-S Bridging Ligands

作　　者：宁宝柱[1] 吴秉芳[2] 刘树堂[2] 胡襄[2] 

机构地区：[1]北京科技大学 [2]内蒙古大学化学系,呼和浩特010021

出　　处：《高等学校化学学报》2001年第8期1286-1289,共4页Chemical Journal of Chinese Universities

基　　金：国家自然科学基金 (批准号 :2 96 6 10 0 1)

摘　　要：[Ru3( CO) 12 ]与 Lawesson试剂 [( Me OC6H4 PS2 ) 2 ]反应 ,合成、分离并用谱学表征了产物三核钌羰合簇[( μ-H) 2 Ru3( CO) 9( μ3-P) ]( )和四核钌羰合簇 [( Ru4 ( CO) 10 ( μ3-S) ( μ3-PC6H4 OMe) ]( ) .X射线衍射测定了 的晶体分子结构 ,表明 含有 1个裸磷原子作为面桥基配体 ,并具有颇短的 Ru— Ru键距 ,该价电子数为4 9e的簇合物对氧和水稳定 .谱学分析表明 ,化合物 具有四面体型的 Ru4 簇心 ,其三角形面上分别具有面桥基 μ3-S和 μ3-PC6H4The reaction of [Ru 3(CO) 12 ] with dimer of p methoxyphenyl thionophosphine sulfide in THF yields the novel trinuclear ruthenium carbonyl cluster [( μ H)] 2Ru 3(CO) 9( μ 3 P)](Ⅰ) and tetranuclear ruthenium carbonyl cluster (Ⅰ) and tetranuclear ruthenium carbonyl cluster [Ru 4(CO) 10 ( μ 3 PC 6H 4OMe)](Ⅱ). These clusters were characterized by elemental analysis, IR, 1H NMR, 31 P NMR and MS spectrometric methods and the molecular structure of compound Ⅰ was determined by X ray diffraction analysis. The molecular geometry of compound Ⅰ contains a trigonal pyramid Ru 3P skeleton with a Ru 3 triangle at the base and the nude phosphorus atom as a 5e μ 3 P bridging ligand at the apex. Though compound Ⅰ is one with 49 valence eletron, its Ru-Ru distances(average 0.283 0 nm) are astonishly short and compound Ⅰ is rather stable in the exposure to oxygen and moisture. The structure of compound Ⅱ is believed to have a tetrahedral Ru 4 core which is attached to a μ 3 S and a μ 3 PC 6H 4OMe ligand on tetrahedron′s two triangular faces.

关 键 词：钌羰基族合物 裸磷原子 含面桥基磷硫配体 晶体结构 

分 类 号：O614.821[理学—无机化学]