稀土金属配合物催化的甲胺基硼烷脱氢聚合反应  

Rare-Earth Metal Complexes-Catalyzed Dehydropolymerization of Methylamine-Boranes

作　　者：蒋胜杰 王杨 徐信 Jiang Shengjie;Wang Yang;Xu Xin(Key Laboratory of Organic Synthesis of Jiangsu Province,College of Chemistry,Chemical Engineering and Materials Science,Soochow University,Suzhou,Jiangsu 215123)

机构地区：[1]苏州大学材料与化学化工学部,江苏省有机合成重点实验室,江苏苏州1215123

出　　处：《有机化学》2023年第5期1786-1791,共6页Chinese Journal of Organic Chemistry

基　　金：国家自然科学基金(No.21871204)资助项目。

摘　　要：报道了稀土金属配合物催化的胺基硼烷脱氢聚合反应.双茂稀土烷基配合物[(C_(5)Me_(4)R)_(2)LnR’,R=Me,H;Ln=Sc,Y;R’=CH_(2)Si Me_(3),CH(SiMe_(3))_(2)]可以有效地实现甲基胺基硼烷(Me NH_(2)·BH_(3),MAB)脱氢反应,生成相应的硼氮聚合物[(Me NH-BH_(2))_(n),PMAB].研究表明随着稀土金属离子半径的增大或者茂基配体空间位阻的减小,聚合活性会随之降低.在机理研究中,通过催化剂与底物的化学计量反应,成功分离得到一例具有β-B-agostic结构的钪胺基硼烷配合物;同时通过控制实验证实了活性的钪氢中间体可能为催化活性物种.Rare-earth metal complexes-catalyzed dehydropolymerization of amine-borane was achieved.Rare-earth metallocene alkyl complexes[(C_5Me_(4)R)_(2)LnR',R=Me,H;Ln=Sc,Y;R'=CH_(2)SiMe_(3),CH(SiMe_(3))_(2)]were found to be active catalysts for the dehydropolymerization of methylamine-borane(MAB),generating corresponding boron-nitrogen polymer[(MeN-HBH_(2))_n,PMAB].The results showed that the polymerization activity would decrease with the increase of ion radius of the metal center or the decrease of the steric hindrance of the supporting ligands.In the mechanistic study,aβ-B-agostic-type scandium amidoborane complex was successfully isolated through the stoichiometric reaction of Sc complex with MAB.Moreover,the control experiment confirmed the existence of scandium hydride species,which may be the catalytic active intermediate.

关 键 词：稀土 胺基硼烷 脱氢 聚合 β-氢消除 

分 类 号：O631.5[理学—高分子化学] O643.36[理学—化学]