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Nitrogen–Carbon Bond Formation by Reactions of a Titanium–Potassium Dinitrogen Complex with Carbon Dioxide, tert ‐Butyl Isocyanate, and Phenylallene
Author(s) -
Nakanishi Yusuke,
Ishida Yutaka,
Kawaguchi Hiroyuki
Publication year - 2017
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.201704286
Subject(s) - chemistry , isocyanate , bifunctional , titanium , potassium , polymer chemistry , ligand (biochemistry) , nitrogen , carbon fibers , medicinal chemistry , inorganic chemistry , organic chemistry , catalysis , materials science , biochemistry , receptor , polyurethane , composite material , composite number
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 CO 2 followed by addition of Me 3 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.