期刊
INORGANICA CHIMICA ACTA
卷 380, 期 -, 页码 336-342出版社
ELSEVIER SCIENCE SA
DOI: 10.1016/j.ica.2011.10.037
关键词
Cooperative catalysis; Copper; Pincer ligand; Click reaction; Ligand design; Hybrid ligand
资金
- Netherlands' Organisation for Scientific Research - Chemical Sciences (NWO-CW) [700.56.403]
- University of Amsterdam
- EU-FP7 COST network [CM0802]
We describe the synthesis and characterization of compound L1H, 2-di(tert-butyl)phosphinomethyl-6-methylpyridine, and the first dimeric Cu-I complex 3 with this novel bidentate NPtBu ligand. We also demonstrate for the first time that this ligand scaffold exhibits noninnocent reactivity through dearomatization behavior, similar to its well-studied tridentate analog L2H, 2,6-bis((di-tert-butylphosphino)methyl)pyridine PNPtBu. The molecular structure of [Cu(CCPh)(L2H)](2) is reported, which is a rare case of a crystallographically characterized copper-acetylide dimer. We also demonstrate that copper(I) complexes with either ligand L1H or L2H or their dearomatized counterparts may act as active, cooperative catalysts for the [2+3] polar cycloaddition of azides and acetylenes. These results represent the first indications of selective Cu-based cooperative catalysis, using non-innocent lutidine-based PNP backbone and catalysts 2 and 5 could thus be termed all-inclusive systems for this reaction. (C) 2011 Elsevier B.V. All rights reserved.
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