Issue 25, 2016

Catalyst design based on agostic interactions: synthesis, characterization, and catalytic activity of bis(pyrazolyl)borate copper complexes

Abstract

Agostic interactions are often used to activate inert C–H bonds, and thus facilitate new reactions. We report the first example of designed catalysts based on the agostic interaction. Novel copper(I) complexes [BBN(pzx)2]Cu(PPh3)n (BBN = 9-borabicyclo[3.3.1]nonane; pzx = 3-substituted pyrazole; x = H, n = 2; x = Me, n = 1) and {[BBN(pziPr)2]Cu}2 have been synthesized and characterized. Single crystal studies of the three compounds show weak intramolecular C–H⋯Cu interactions which can be assigned as agostic or anagostic interactions. Catalytic studies of these complexes toward carbenoid insertion into N–H bonds indicate these weak interactions act as a “switch” which will be turned “on” if interacting with the substrate and “off” if eliminating the product and regenerating the weak interaction. The process of the “switch” turning “on” or “off”, which is related to the catalytic effect, is found to be influenced by both steric effects and the solvent: a less sterically hindered catalyst in non-coordinating benzene results in high yield, while a more sterically hindered catalyst in coordinating THF results in relatively low yield.

Graphical abstract: Catalyst design based on agostic interactions: synthesis, characterization, and catalytic activity of bis(pyrazolyl)borate copper complexes

Supplementary files

Article information

Article type
Paper
Submitted
02 Apr 2016
Accepted
28 Apr 2016
First published
28 Apr 2016

Dalton Trans., 2016,45, 10194-10199

Catalyst design based on agostic interactions: synthesis, characterization, and catalytic activity of bis(pyrazolyl)borate copper complexes

H. Cao, Q. Zhao, Q. Zhang, J. Li, E. J. M. Hamilton, J. Zhang, L. Wang and X. Chen, Dalton Trans., 2016, 45, 10194 DOI: 10.1039/C6DT01272H

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