Published August 26, 2015
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Reversible 1,2-Alkyl Migration to Carbene and Ammonia Activation in an N-Heterocyclic Carbene–Zirconium Complex
Abstract
Addition of trimethylphosphine to a bis(phenolate)benzylimidazolylidene(dibenzyl)zirconium complex induces migration of a benzyl ligand from the metal center to the C_(carbine) atom. This process may be reversed, resulting in C_(sp)^3–C_(sp)^3 activation, by abstraction of the phosphine, an example of regulated, reversible alkyl migration. Addition of ammonia to the dibenzyl complex results in migration of one benzyl group and protonolysis of the other to generate a bis(NH_2)-bridged dimer via an NMR-observable intermediate NH_3 adduct.
Additional Information
© 2015 American Chemical Society. Received: June 28, 2015; Published: August 7, 2015. This work was supported by the U.S. DOE, Office of Basic Energy Sciences (Grant DE-FG03-85ER13431). The Bruker KAPPA APEXII X-ray diffractometer was purchased via an NSF CRIF:MU award to the California Institute of Technology (CHE-0639094). The authors declare no competing financial interest.Attached Files
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Additional details
- Eprint ID
- 60306
- Resolver ID
- CaltechAUTHORS:20150917-154149857
- DE-FG03-85ER13431
- Department of Energy (DOE)
- CHE-0639094
- NSF
- Created
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2015-09-17Created from EPrint's datestamp field
- Updated
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2021-11-10Created from EPrint's last_modified field