闭式十二顶双镍十硼烷簇合物[(μ-Cl)(Ph_2PC_6H_4)_2Ni_2B_(10)H_6Cl(PPh_3)]的合成与结构

Synthesis and Crystal Structure of closo Twelve-vertex Cluster [(μ-Cl)(Ph_2PC_6H_4)_2Ni_2B_(10 )H_6Cl(PPh_3)]

研究了 [NiX2 (PPh3 ) 2 ](X =F ,Cl,SCN)在二氯甲烷中与B10 H2 -10 的反应 ,对形成的产物 [(μ Cl) (Ph2 PC6H4) 2 Ni2 B10 H6Cl(PPh3 ) ]·0 2 5CH2 Cl2 (1)通过元素分析、红外光谱、飞行时间二次离子质谱等进行了表征 ,并通过单晶X射线衍射测定了簇合物的结构 .1的晶体学数据 :单斜晶系 ,空间群P2 1/c,a =1 170 3(2 )nm ,b =2 10 82 (4)nm ,c=2 2 0 6 8(8)nm ,β =99 98(2 )°,V =5 36 2 2 (2 )nm3 ,Z =4 ,F(0 0 0 ) =2 2 74 ,Dcalcd=1 373g/cm3 .R1=0 0 35 8,wR2 =0 0 80 7.1为闭式十二顶双镍十硼烷簇合物 ,具有两个邻位环化的Ni—P—C—C—B五元环 ,镍 -镍之间还存在氯桥 .结构分析表明 :邻位环化增强了镍与硼之间的成键作用 .

The reactions of [NiX 2(PPh 3) 2] (X=F, Cl, SCN) with B 10 H 2- 10 in CH 2Cl 2 were investigated and the cluster [(μ Cl)(Ph 2PC 6H 4) 2Ni 2B 10 H 6Cl(PPh 3)]·0 25CH 2Cl 2 (1) was characterized by elemental analysis, IR, time of flight secondary ion mass spectrum and single crystal diffraction analysis. Crystal data for 1: triclinic crystal system, space group P 2 1/ c with cell dimensions, a =1 1703(2) nm, b =2 1082(4) nm, c =2 2068(8) nm, β =99 98(2)°, V =5 3622(2) nm 3, Z =4, F (000)=2274, D calcd =1 373 g/cm 3. R 1=0 0358, wR 2=0 0807. The cluster possesses closo twelve vertex configuration and has two ortho cycloboronated Ni-P-C-C-B five membered rings. There is a Cl bridge between two Ni atoms. The structure analysis shows that the cyclization can strengthen the nickel to boron bonding.