期刊
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
卷 56, 期 31, 页码 9193-9197出版社
WILEY-V C H VERLAG GMBH
DOI: 10.1002/anie.201704286
关键词
nitrogen fixation; O ligands; potassium; titanium; tripodal ligands
资金
- Ministry of Education, Culture, Sports, Science and Technology, Japan [15H00927]
- JST ACT-C Grant [JPMJCR12YA]
- Grants-in-Aid for Scientific Research [15H00927] Funding Source: KAKEN
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-2 atmosphere to generate a bifunctional complex (2) in which N-2 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 CO2 followed by addition of Me3SiCl 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.
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