Carbon dioxide cleavage by a Ni_2 complex supported by a binucleating bis(N-heterocyclic carbene) framework

Creators: Tsui, Emily Y.; Agapie, Theodor

Abstract

A binucleating bis(N-heterocyclic carbene) ligand was designed as a means to coordinate and proximally constrain two transition metal centers. Using an imidazopyridine-based NHC afforded a framework structurally related to previously reported para-terphenyl diphosphines. Bimetallic copper, cobalt, and nickel complexes supported by this framework were synthesized and structurally characterized. Strong interactions between the metal centers and the central arene were observed in all nickel complexes. Dinickel(0) complexes of this ligand framework were found to react with CO_2 to form a dicarbonyl-bridged dinickel(0) product, demonstrating facile CO_2 reduction.

Additional Information

© 2014 Elsevier Ltd. Received 6 May 2014; Accepted 18 June 2014; Available online 2 July 2014. This work was supported by the California Institute of Technology, NSF CAREER Grant CHE-1151918 (to T.A.), and a Sandia Campus Executive Fellowship (to E.Y.T.). TA is a Sloan, Cottrell, and Dreyfus fellow. We thank L. M. Henling for assistance with crystallography. The Bruker KAPPA APEXII X-ray diffractometer was purchased via an NSF Chemistry Research Instrumentation award to Caltech (CHE-0639094). The 400 MHz NMR spectrometer was purchased via NIH Award RR027690.

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