Reactions of the [Ni6(CO)12]2- dianion with stibine and bismuthine reagents: synthesis and stereophysical characterization of the [Ni10(SbPh)2(CO)18]2- dianion containing a noncentered icosahedral Ni10Sb2 core and Ni2(CO)4(μ2-Ph2SbOSbPh2)2 containing a centrosymmetric eight-membered (NiSbOSb)2 ring
作者:Robert E. DesEnfants、James A. Gavney、Randy K. Hayashi、A.David Rae、Lawrence F. Dahl、Asgeir Bjarnason
DOI:10.1016/0022-328x(90)85153-p
日期:1990.2
unambiguously established from X-ray crystallographic determinations of four different ionic compounds, viz., [NMe4]+2 [2]2- · 2THF (2a), [NMe4]+2 [2]2- · 2Me2CO (2b), [(Ph3P)2N]+2 [2]2- · 2THF (2c), and [NMe3Ph]+2 [2]2- (2d). In each salt, the geometrically similar nickel stibinidene carbonyl dianion possesses a closo 1,12-disubsituted, icosahedral Ni10Sb2 core, (i.e., a bi-Sb-capped pentagonal-antiprismatic
在进一步研究可从富含电子的[Ni 6(CO)12 ] 2-二价阴离子(1)进入的高核混合金属(主族)簇的类型时,反应1(氢的直接后代)已经用锑和铋试剂进行了反应。[Ni 10(SbPh)2(CO)18 ] 2-在室温下于THF溶液中与1的二氯苯基二苯乙烯(Ph 2 SbCl)或二氯苯基二苯乙烯(PhSbCl 2)的反应以50–60%的产率分离出的主要产物。二价阴离子(2); 它的身份明确地由X射线晶体学测定的四种不同离子化合物确定,即[NMe 4 ] + 2 [ 2 ] 2- ·2THF(2a),[NMe 4 ] + 2 [ 2 ] 2- ·2Me 2 CO(2b),[(Ph 3 P)2 N] + 2 [ 2 ] 2- ·2THF(2c)和[NMe 3 Ph] + 2 [ 2 ] 2-(2d)。在每种盐,所述几何形状类似镍stibinidene羰基二价阴离子具有一个闭合碳1,12-二取代,二十面体的Ni