multinuclear NMR spectroscopy. Both steric and electronic factors are important in determining the structural motif (CT vs. ionic) observed in the solid-state. In general, highly basic phosphines result in a lengthening of the Se-I interaction, and a preference for an ionic structure. The reaction with (o-CH(3)C(6)H(4))(3)P does not yield a stable R(3)PSe(Ph)I adduct, and instead (o-CH(3)C(6)H(4))(3)PI(2)
研究了(Ph(2)Se(2)I(2))(2)与具有不同空间和电子性质的多种叔膦的反应,在大多数情况下导致R(3)PSe(Ph)我加成;[R(3)P =(p-CH(3)C(6)H(4))(3)P(1),(m-CH(3)C(6)H(4))(3) P(2),(邻-OCH(3)C(6)H(4))(3)P(4),Ph(2)MeP(6),Me(2)PhP(7),Me(3 )P(8),Cy(3)P(9)]。通过元素分析,拉曼光谱和多核NMR光谱对所有形成的产物进行表征。空间和电子因素在确定固态中观察到的结构基序(CT与离子)方面均很重要。通常,高度碱性的膦导致Se-1相互作用的延长,并且优先选择离子结构。与(o-CH(3)C(6)H(4))(3)P的反应不会产生稳定的R(3)PSe(Ph)I加合物,而是(o-CH(3)C(形成6)H(4))(3)
PI(2)(3)。所显示的异常长的
PI键[2.5523(12)A]和短的II键[3