三丁基膦亚胺（tBu2PNP（I）tBu2）和 EPR2NP（I）R2（E = Se，Te；R = iPr，tBu）的合成、多核 NMR 谱和 X 射线结构。

Synthesis, multinuclear NMR spectra, and X-ray structures of tBu2PNP(I)tBu2 and EPR2NP(I)R2 (E = Se, Te; R = iPr, tBu).

机构信息

Department of Chemistry, University of Calgary, Calgary T2N 1N4, Alberta, Canada.

出版信息

Inorg Chem. 2010 May 17;49(10):4681-6. doi: 10.1021/ic1005055.

PMID:20402473

Abstract

Two synthetic routes to bifunctional P(V)/P(V) compounds of the type EPR(2)NP(I)R(2) have been developed. The reaction of Li[EP(i)Pr(2)NP(i)Pr(2)] with one molar equivalent of I(2) produces EP(i)Pr(2)NP(I)(i)Pr(2) (3a-I, E = Se; 3b-I, E = Te). Alternatively, the oxidation of Na[N(P(t)Bu(2))(2)] with I(2) in tetrahydrofuran (THF) generates the P(III)/P(V) compound (t)Bu(2)PNP(I)(t)Bu(2) (6'-I) which, on treatment with elemental selenium or tellurium in THF, yields EP(t)Bu(2)NP(I)(t)Bu(2) (3a'-I, E = Se; 3b'-I, E = Te). The acyclic compounds 3a-I, 3a'-I, 3b-I, 3b'-I, and 6'-I have been characterized in solution by multinuclear ((1)H, (31)P, (77)Se, and (125)Te) NMR spectroscopy and in the solid state by X-ray structural determinations.

摘要

已经开发出两种将双官能 P(V)/P(V) 化合物 EPR(2)NP(I)R(2)合成的方法。反应 Li[EP(i)Pr(2)NP(i)Pr(2)]与一摩尔当量的 I(2)产生 EP(i)Pr(2)NP(I)(i)Pr(2) (3a-I，E = Se；3b-I，E = Te)。或者，在四氢呋喃 (THF) 中用 I(2)氧化 Na[N(P(t)Bu(2))(2)]生成 P(III)/P(V)化合物 (t)Bu(2)PNP(I)(t)Bu(2) (6'-I)，然后在 THF 中用元素硒或碲处理，得到 EP(t)Bu(2)NP(I)(t)Bu(2) (3a'-I，E = Se；3b'-I，E = Te)。无环化合物 3a-I、3a'-I、3b-I、3b'-I 和 6'-I 在溶液中通过多核 ((1)H、(31)P、(77)Se 和 (125)Te) NMR 光谱和在固态通过 X 射线结构测定进行了表征。