A Two-Coordinate Nickel Imido Complex That Effects C-H Amination

Description:

This article discusses a two-coordinate nickel imido complex that effects C-H amination.

Creator(s):
Creation Date: December 22, 2010
Partner(s):
UNT College of Arts and Sciences
Collection(s):
UNT Scholarly Works
Usage:
Total Uses: 71
Past 30 days: 1
Yesterday: 0
Creator (Author):
Laskowski, Carl A.

University of Chicago

Creator (Author):
Miller, Alexander J.M.

California Institute of Technology

Creator (Author):
Hillhouse, Gregory L.

University of Chicago

Creator (Author):
Cundari, Thomas R., 1964-

University of North Texas

Publisher Info:
Publisher Name: American Chemical Society
Place of Publication: [Washington, D.C.]
Date(s):
  • Creation: December 22, 2010
Description:

This article discusses a two-coordinate nickel imido complex that effects C-H amination.

Degree:
Department: Chemistry
Note:

Reprinted with permission from the Journal of the American Chemical Society. Copyright 2010 American Chemical Society.

Note:

Abstract: An exceptionally low coordinate nickel imido complex, (IPr*)Ni=N(dmp) (2) (dmp=2,6-dimesitylphenyl), has been prepared by the elimination of N₂ from a bulky aryl azide in its reaction with (IPr*)Ni(ɳ⁶-C₇H₈) (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=CH₂) (5) via an azanickelacyclobutane intermediate, (IPr*)Ni{N,C:k²-N(dmp)CH₂CH₂} (4).

Physical Description:

3 p.

Language(s):
Subject(s):
Keyword(s): nickel | imido | low-coordinate | density functional theory
Source: Journal of the American Chemical Society, 2010, Washington DC: American Chemical Society, pp. 771-773
Partner:
UNT College of Arts and Sciences
Collection:
UNT Scholarly Works
Identifier:
  • DOI: 10.1021/ja1101213 |
  • ARK: ark:/67531/metadc107785
Resource Type: Article
Format: Text
Rights:
Access: Public
Citation:
Publication Title: Journal of the American Chemical Society
Volume: 133
Issue: 4
Page Start: 771
Page End: 773
Peer Reviewed: Yes