A Two-Coordinate Nickel Imido Complex That Effects C−H Amination
Abstract
An exceptionally low coordinate nickel imido complex, (IPr*)Ni═N(dmp) (2) (dmp = 2,6-dimesitylphenyl), has been prepared by the elimination of N_2 from a bulky aryl azide in its reaction with (IPr*)Ni(η^6-C_7H_8) (1). The solid-state structure of 2 features two-coordinate nickel with a linear C−Ni−N core and a short Ni−N distance, both indicative of multiple-bond character. Computational studies using density functional theory showed a Ni═N bond dominated by Ni(dπ)−N(pπ) interactions, resulting in two nearly degenerate singly occupied molecular orbitals (SOMOs) that are Ni−N π* in character. Reaction of 2 with CO resulted in nitrene-group transfer to form (dmp)NCO and (IPr*)Ni(CO)_3 (3). Net C−H insertion was observed in the reaction of 2 with ethene, forming the vinylamine (dmp)NH(CH═CH_2) (5) via an azanickelacyclobutane intermediate, (IPr*)Ni{N,C:κ^2-N(dmp)CH_2CH_2} (4).
Additional Information
© 2011 American Chemical Society. Received: November 10, 2010. Article ASAP December 22, 2010. Published In Issue February 02, 2011. This work was supported by the National Science Foundation through Grants CHE-0957816 (to G.L.H.) and CHE-0741936 (equipment, to T.R.C.), the Office of Basic Energy Sciences, Department of Energy, through Grant DEFG02-03ER15387 (to T.R.C.), and the MMRC of the Beckman Institute. A.J.M.M. thanks the Gordon and Betty Moore Foundation for support.Attached Files
Supplemental Material - ja1101213_si_001.pdf
Supplemental Material - ja1101213_si_002.cif
Files
Name | Size | Download all |
---|---|---|
md5:0f0e6d3a0ffba37afcc1cadf85e21bd0
|
84.8 kB | Download |
md5:b019ceeff95132641bf4b21d6a276a75
|
3.6 MB | Preview Download |
Additional details
- Eprint ID
- 23025
- Resolver ID
- CaltechAUTHORS:20110322-085930444
- CHE-0957816
- NSF
- CHE-0741936
- NSF
- DEFG02-03ER15387
- Department of Energy (DOE) Office of Basic Energy Sciences
- Caltech Beckman Institute Molecular Materials Research Center (MMRC)
- Gordon and Betty Moore Foundation
- Created
-
2011-03-22Created from EPrint's datestamp field
- Updated
-
2021-11-09Created from EPrint's last_modified field