Study on Synthesis and Properties of Functional Material Poly [Sila (N-Substituted) Imine]

本文研究了钯催化的异腈在低聚硅烷硅-硅键上的插入反应。在四（三苯基膦）钯（O）配合物或乙酸钯（II）存在下，各种乙硅烷与脂肪族和芳香族异腈反应，以中等产率得到相应的双（硅基）N-取代亚胺。在乙酸钯（II）的存在下，使低聚硅烷与过量的2，6-二取代的芳基异氰化物反应，导致异氰化物规则地插入到每个硅-硅键中，得到聚（硅亚胺）衍生物。钯催化的规则插入成功地实现了高达六硅烷。通过使用有限量的异氰化物，也可以选择性地将异氰化物部分插入到低聚硅烷中。在钯催化下，四硅烷与1摩尔当量的2，6-二取代苯基异腈反应生成2，4-二硅杂-3，3-双（硅烷基）-1-氮杂环丁烷衍生物，该衍生物由四个四硅烷片段和两个异腈片段重组而成。值得注意的是，在钯催化剂上的叔烷基异腈配体有助于骨架重排。

Palladium-catalyzed insertion reactions of isocyanides into silicon-silicon linkage of oligosilanes have been studied. A variety of disilanes reacted with aliphatic and aromatic isocyanides in the presence of palladium (O) tetrakis (triphenylphosphine) complex or palladium (II) acetate to give the corresponding bis (silyl) N-substituted imines in moderate yields. Oligosilanes were reacted with an excess of 2, 6-disubstituted aryl isocyanide in the presence of palladium (II) acetate, resulting in regular insertion of the isocyanide into each silicon-silicon linkage giving poly (silaimine) derivatives. The palladium catalyzed regular insertion was successfully achieved with up to hexasilane. Partial insertion of the isocyanide into oligosilanes was also achieved selectively by use of the limiting amount of isocyanide. New skeletal rearrangement of tetrasilanes was found in the palladium catalyzed reaction of tetrasilanes with one molar equivalent of 2, 6-disubstituted phenyl isocyanide to afford 2, 4-disila-3, 3-bis (silyl)-1-azacyclobutane derivatives, which was properly reconstituted from four fragments of tetrasilane and two fragments of isocyanide. Noteworthy is that the skeletal rearrangement was assisted by tert-alkyl isocyanide ligand on palladium catalyst.