s-Block carbodicarbene chemistry: C(sp(3))-H activation and cyclization mediated by a beryllium center

Walley, Jacob E; Breiner, Grace; Wang, Guocang; Dickie, Diane A; Molino, Andrew; Dutton, Jason; Wilson, David; Gilliard, Robert J

doi:10.26181/608b6a5a85e21

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s-Block carbodicarbene chemistry: C(sp(3))-H activation and cyclization mediated by a beryllium center

journal contribution

posted on 2021-04-30, 02:24 authored by Jacob E Walley, Grace Breiner, Guocang Wang, Diane A Dickie, Andrew MolinoAndrew Molino, Jason DuttonJason Dutton, David WilsonDavid Wilson, Robert J Gilliard

The first examples of carbodicarbene (CDC)-s-block complexes have been synthesized. The addition of base or reducing agent to a CDC-beryllium (chloride)(hexamethyldisilazide) adduct results in the unprecedented activation of a pendant C(sp )-H bond and cyclization of the CDC to form a five-membered beryllium metallacycle. This also represents the first example of chemical activation of a CDC which transforms the ligand from monodentate neutral to chelating anionic.

Funding

The authors are grateful to the University of Virginia for support of this work. We also thank Xiaofan Jia for assistance with large scale hydrogenation reactions necessary for ligand preparation. Generous allocation of computing resources from National Computational Infrastructure (NCI) and La Trobe University are acknowledged.

History

Publication Date

2019-01-01

Journal

Chemical Communications

Volume

55

Issue

13

Pagination

4p. (p. 1967-1970)

Publisher

Royal Society of Chemistry (RSC)

ISSN

1359-7345

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