Department of Chemistry, Tokyo Institute of Technology, Ookayama, Meguro-ku, Tokyo, 152-8551, Japan.
Angew Chem Int Ed Engl. 2017 Jul 24;56(31):9193-9197. doi: 10.1002/anie.201704286. Epub 2017 Jun 14.
Nitrogen-carbon bond-forming reactions at coordinated dinitrogen in a bifunctional titanium-potassium system are reported. A titanium atrane complex with a tris(aryloxide)methyl ligand (1) was treated with two equivalents of potassium naphthalenide under N atmosphere to generate a bifunctional complex (2) in which N binds end-on to two titanium centers and side-on to three potassium cations. Dinitrogen complex 2 reacted with carbon dioxide, tert-butyl isocyanate, and phenylallene, forming nitrogen-carbon bonds and affording diverse N-functionalized products. The reaction of 2 with CO followed by addition of Me SiCl resulted in the formation of the starting complex 1 with concomitant release of silylated carboxyl hydrazines while the reaction with two equivalents of tert-butyl isocyanate proceeded by insertion into the Ti-N bonds. Treatment of 2 with phenylallene afforded vinyl-substituted hydrazido complexes.
报道了在双功能钛-钾体系中配位二氮分子中形成氮-碳键的反应。用两当量的萘基钾处理带有三（芳氧基）甲基配体的钛环戊二烯配合物（1），在氮气气氛下生成双功能配合物（2），其中 N 以端到端的方式结合到两个钛中心，以侧到侧的方式结合到三个钾阳离子。二氮配合物 2 与二氧化碳、叔丁基异氰酸酯和苯丙二烯反应，形成氮-碳键，并得到多种 N-官能化产物。2 与 CO 的反应，随后加入 MeSiCl，导致起始配合物 1 的形成，同时伴随着甲硅烷基化的羧基腙的释放，而与两当量的叔丁基异氰酸酯的反应则通过插入 Ti-N 键进行。用苯丙二烯处理 2 得到了乙烯基取代的腙配合物。
