作者:Adam D. Gorman、Jessica A. Cross、Rachel A. Doyle、Tom R. Leonard、Paul G. Pringle、Hazel A. Sparkes
DOI:10.1002/ejic.201900032
日期:2019.3.31
Phosphophosphidites of the type R2P–P(binol) [where binol = the dianion of (S)‐1,1′‐bi‐2‐naphthol] are the phosphorus analogues of the ubiquitous phosphoramidites, R2N–P(binol) and are readily accessed by the chlorosilane elimination reaction between R2P–SiMe3 and Cl–P(binol). The crystal structure of iPr2P–P(binol) (1) has been determined and shows a P–P bond length in the normal range. The solution
R 2 P–P(binol)类型的亚磷酸酯[其中binol =(S)-1,1'-bi-2-萘酚的二价阴离子]是普遍存在的亚磷酰胺的磷类似物,R 2 N–P(binol) ),并且很容易通过R 2 P–SiMe 3和Cl–P(binol)之间的氯硅烷消除反应来获得。确定了i Pr 2 P–P(binol)(1)的晶体结构,并显示了正常范围内的P–P键长。主要通过31 P NMR光谱研究了1的溶液反应,结果表明:(a)与亚磷酰胺相反,1对水分极为敏感;(b)在P-P键1时用H反应被裂解2 O,MeOH或酚; (c)与吡咯烷反应时,1中的P–O键断裂;(d)与BH 3或Mo 0配合时,1的完整性得以保留。顺式-[Mo(CO)4(1)2 ]的晶体结构表明1在P(binol)位点与Mo结合,而v CO为2032 cm -1则表明1具有与a相似的配体性质。亚膦酸酯。