摘要
研究了[NiX_2(PPh_3)_2](X=Br,I)在二氯甲烷等溶剂中与B_(10)H_(10)^(2-)的反应,对形成的簇合物[(μ-Br_(0.85)Cl_(0.15)-(Ph_2PC_6H_4)_2Ni_2B_(10)Cl(PPh_3)] ·0.5CH_2Cl_2(1),[(μ-I_(0.1)Cl_(0.9))(Ph_2PC_6H_4)_2Ni_2B_(10)H_6Cl(PPh_3)]·0.25CH_2Cl_2(2)进行了元素分析、红外光谱、飞行时间二次离子质谱和X射线单晶结构分析等表征.两个簇合物均为闭式十二顶双镍十硼烷,镍、镍之间还分别存在Cl,Br和Cl,I桥且Cl,Br或I的占有率不同.簇合物还具有两个邻位环化的Ni-P-C-C-B五元环.研究结果进一步证实:阴离子对反应产物有影响,二氯甲烷参与了反应.
The reactions of [NiX2(PPh3)(2)](X = Br, I) with B10H102- in CH2Cl2 are investigated and the clusters [(muBr(0.85)Cl(0.15))(Ph2PC6H4)(2)Ni2B10H6Cl(PPh3)].0.5CH(2)Cl(2) (1), [(mu-I0.1Cl0.9)(Ph2PC6H4)(2)Ni2B10H6Cl (PPh3)] . 0.25CH(2)Cl(2) (2) have been characterized by elemental analysis, IR, time-of-flight secondary ion mass spectrum and single crystal diffraction analysis. Two clusters are monoclinic crystal system, space group P2(1)/c with cell dimensions, 1 a = 1.1703(2) nm, b =2.1082(4) nm, c =2.2068(8) run, beta=99.98(2)degrees, 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 and 2 a = 1:1732 (4), b = 2.1123(8), c =2.2088(10) nm, beta=99.90(3)degrees, V=5.392(4) nm(3), Z=4, F(000) = 2288, D-calcd = 1.377 g/cm3, R-1 = 0.0557, wR(2) = 0.1085. The clusters are closo twelve-vertex configuration and have two ortho-cycloboronated Ni-P-C-C-B five-membered rings respectively. There are Cl-, Br- or I-mixed-bridges between two Ni atoms. The structure analysis shows that cyclization can strengthen the nickel-to-boron bonding and CH2Cl2 can partake in reactions.
出处
《化学学报》
SCIE
CAS
CSCD
北大核心
2003年第7期1006-1013,共8页
Acta Chimica Sinica
基金
国家自然科学基金(No.29873009)
山东省自然科学基金(No.Q99B04)
