Synthesis and Structure of Pentavalent Bismuth(V) Alkoxides and Ligand Redistribution Equilibria in Solution
作者:Silke Hoppe、Kenton H. Whitmire
DOI:10.1021/om970760r
日期:1998.3.1
The six new pentavalent Bi(V) alkoxide complexes Ph3Bi(OR)2, 1, Ph3BiBr(OR), 2, and Ph4Bi(OR), 3 (a, R = C6F5; b R = C6Cl5) have been prepared. Ph4Bi(OR) was synthesized by alcoholysis of BiPh5 with ROH. Ph3Bi(OR)2 and Ph3BiBr(OR) were products of the salt elimination reaction between Ph3BiBr2 and NaOR. These compounds were characterized spectroscopically and by single-crystal X-ray diffraction. In
的六个新的五价铋(V)醇盐络合物博士3的Bi(OR)2,1中,Ph 3 BIBR(OR),2或Ph 4毕(OR),3(一个,R = C 6 ˚F 5 ; b ř = C 6 Cl 5)已经准备好。Ph 4 Bi(OR)是由BiPh 5与ROH醇解合成的。Ph 3 Bi(OR)2和Ph 3 BiBr(OR)是Ph 3 BiBr 2之间的盐消除反应的产物和NaOR。这些化合物通过光谱学和单晶X射线衍射表征。在固态下,它们具有扭曲的三角双锥体配位几何形状。虽然混合物种博士3 BIBR(OR)可以以纯的形式,为结晶固体被分离,它们不作为纯化合物在溶液中由于非常快速再分布平衡pH存在3的Bi(OR)2 +博士3 BIBR 2 ⇌2PH 3 BiBr(OR)。使用VT NMR光谱法测量平衡常数。为了比较,二卤化物Ph 3 BiX 2之间先前未报告的交叉交换反应的平衡常数(X = F,Cl,Br)也在226