A Discrete N,O,N-Supported Gallium Amido Complex for the Intermolecular Hydroamination of Terminal Alkynes

作者：Hild Frederic; Dagorne Samuel^*

来源：Organometallics, 2012, 31(3): 1189-1194.

DOI：10.1021/om2012584

The diamino-ether ligand {(C5H9)NH-C6H4}(2)O (1) was found to readily react with 0.5 equiv of Ga-2(NMe2)(6) via an amine elimination route to afford the N,O,N-supported Ga amido species (eta(3)-N,O,N-((C5H9)N-C6H4)(2)O}GaNMe2 (2) in a reasonable yield (51%). As determined by X-ray crystallography, the four-coordinate Ga center in 2 adopts an unusual trigonal-monopyramidal geometry. Compound 2 effectively catalyzes the hydroamination of terminal alkynes (such as 1-hexyne and phenylacetylene) in the presence of primary amines (aniline and butylamine). Kinetic studies on the latter catalytic reactions suggest that these proceed with a first-order rate dependence on alkyne and on species 2. In preliminary studies aiming at the isolation of intermediates relevant to the present catalysis, the dimeric Ga complex [{eta(2)-N,N-((C5H9)N-C6H4)(2)O}Ga(mu-NHPh)](2) (3) was synthesized by an aminolysis reaction between compound 2 and aniline; its identity was confirmed by X-ray crystallographic analysis.

• 出版日期2012-2-13