含偶磷氮烷配体的三核钌羰基簇合物的合成和晶体结构  

Synthesis and Crystal Strrctures of Trinuclear Ruthenium Carbonyl Clusters C ontaining Cyclodiphosphazane Ligand

作　　者：宫培军[1] 吴秉芳[1] 刘树堂[1] 王丁泽[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》2004年第1期37-40,共4页Chinese Journal of Inorganic Chemistry

基　　金：国家自然科学基金资 助项目(No.29861001);内蒙古自治区高等学校科学基金项目(No.ZD01701)资助。

摘　　要：用Ru 3 (CO) 12 与顺-2,4二(叔丁基胺基)-1,3,-二(叔丁基)-1,3,2,4-环偶磷氮烷cis-[P(NHBu t )NBu t ] 2 反应,得到两个新的含偶磷氮环的三核钌羰基簇合物:Ru 3 (CO) 11 [{P(NHBu t )NBu t } 2 ]Ⅰ和Ru 3 (CO) 11 [P(NHBu t )(NBu t ) 2 P(O)H]Ⅱ。对它们进行了元素分析,IR和 1 H NMR谱表征,并用X-ray单晶衍射法测定了晶体结构。Ⅰ:正交晶系,Pna2(1)空间群,a= 2.7574(9)nm,b=0.8981(3)nm,c=1.5272(5)nm,V=3.782(2)nm 3 ,D c =1.686g·cm -3 ,Z=4;Ⅱ:三斜晶系,P1空间群,a=0.96384(19)nm,b=1.1705(2)nm,c=1.5589(3)nm,α=101 .72(3)°,β=91.54(3)°,γ=108.20(3)°,V=1.6282(6)nm 3 ,D c =1.845g·cm -3 ,Z=2;两个簇合物均为Ru 3 (CO) 12 的单取代衍生物,配位基环偶磷氮烷以单齿P原子配位在一个Ru原子的赤道位置上。Ⅱ中 ,偶磷氮环上未配位P被氧化成具有膦酰基结构(=P(O)H)的P。Reaction of Ru 3 (CO) 12 with cis - 2,4 - di(tert - butylamino) - 1,3 - di(tert - butyl) - 1,3,2,4 - cyclodiphosph - azane,yielded two novel trinuclear ruthenium carbonyl clusters containing cyclodiphosphazane ligand:Ru 3 (CO) 11 [{P(NHBu t )NBu t } 2 ](Ⅰ)and Ru 3 (CO) 11 [P(NHBu t )(NBu t ) 2 P(O)H](Ⅱ).These complexes have been characterized by elementary analysis,IR and 1 H NMR spectra and X - ray single crystal diffraction.Ⅰ:Orthorhombic,Pna2 1 ,a=2.7574(9)nm,b=0.8981(3)nm,c=1.5272(5)nm,V=3.782(2)nm 3 ,D c =1.686g · cm -3 ,Z=4;Ⅱ:triclinic,P1,a=0.96384(19)nm,b=1.1705(2)nm,c=1.5589(3)nm,α =101.72(3) ° ,β =91.54(3) ° ,γ =108.20(3) ° ,V=1.6282(6)nm 3 ,D c =1.845g · cm -3 ,Z=2;In two complexes,the phosphorus - nitrogen heterocycle is not cleaved during the reactions,and one P atom of t hem is coordinated to Ru atom.In the complexⅡ,the uncoordinated Patom was oxi dized to the Phosphonic amide=P(O)H,in which process the bond between P and NHBu t group was cleaved and one P - H bond was formed.CCDC:Ⅰ,217283;Ⅱ,217282.

关 键 词：环偶磷氮烷配体 三核钌羰基簇合物 合成 晶体结构 X射线衍射法 

分 类 号：O614.821[理学—无机化学] O641.4[理学—化学]