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Title: Clusters containing carbene ligands. The formation of a carbene ligand by C-H activation of a. pi. -complexes iminium ligand

Abstract

Recently, there has been a flurry of interest in the nature of the activation of olefinic CH bonds by metal complexes. Studies have shown that the barriers to the activation of CH bonds of ..pi..-complexed olefins by mononuclear metal complexes are very large. Indeed, evidence has been presented which demonstrates that olefinic CH activation by certain mononuclear metal complexes occurs without precoordination of the olefin. By contrast olefininc CH activation by polynuclear metal complexes and on surfaces is a relatively facile process. In these cases, it is believed that the activation step is a two-center process in which the olefin is coordinated to one metal atom and the CH cleavage takes place by interaction at a vacant coordination site on a neighboring metal atom. Iminium ions, H/sub 2/C=NR/sub 2//sup +/, are isoelectronic to olefins, and they are known to form ..pi..-bonded complexes analogous to ..pi..-olefin complexes. In this communication is described the first example of a C-H activation of a ..pi..-complexed iminium ion and its conversion into a dialkylaminocarbene ligand.

Authors:
;
Publication Date:
Research Org.:
Univ. of South Carolina, Columbia
OSTI Identifier:
5572296
Resource Type:
Journal Article
Journal Name:
J. Am. Chem. Soc.; (United States)
Additional Journal Information:
Journal Volume: 109:22
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; CARBENES; CHEMICAL REACTIONS; IMINES; CARBON; CHEMICAL BONDS; EXPERIMENTAL DATA; HYDROGEN; LIGANDS; DATA; ELEMENTS; INFORMATION; NONMETALS; NUMERICAL DATA; ORGANIC COMPOUNDS; ORGANIC NITROGEN COMPOUNDS; RADICALS; 400201* - Chemical & Physicochemical Properties

Citation Formats

Adams, R D, and Babin, J E. Clusters containing carbene ligands. The formation of a carbene ligand by C-H activation of a. pi. -complexes iminium ligand. United States: N. p., 1987. Web. doi:10.1021/ja00256a063.
Adams, R D, & Babin, J E. Clusters containing carbene ligands. The formation of a carbene ligand by C-H activation of a. pi. -complexes iminium ligand. United States. https://doi.org/10.1021/ja00256a063
Adams, R D, and Babin, J E. 1987. "Clusters containing carbene ligands. The formation of a carbene ligand by C-H activation of a. pi. -complexes iminium ligand". United States. https://doi.org/10.1021/ja00256a063.
@article{osti_5572296,
title = {Clusters containing carbene ligands. The formation of a carbene ligand by C-H activation of a. pi. -complexes iminium ligand},
author = {Adams, R D and Babin, J E},
abstractNote = {Recently, there has been a flurry of interest in the nature of the activation of olefinic CH bonds by metal complexes. Studies have shown that the barriers to the activation of CH bonds of ..pi..-complexed olefins by mononuclear metal complexes are very large. Indeed, evidence has been presented which demonstrates that olefinic CH activation by certain mononuclear metal complexes occurs without precoordination of the olefin. By contrast olefininc CH activation by polynuclear metal complexes and on surfaces is a relatively facile process. In these cases, it is believed that the activation step is a two-center process in which the olefin is coordinated to one metal atom and the CH cleavage takes place by interaction at a vacant coordination site on a neighboring metal atom. Iminium ions, H/sub 2/C=NR/sub 2//sup +/, are isoelectronic to olefins, and they are known to form ..pi..-bonded complexes analogous to ..pi..-olefin complexes. In this communication is described the first example of a C-H activation of a ..pi..-complexed iminium ion and its conversion into a dialkylaminocarbene ligand.},
doi = {10.1021/ja00256a063},
url = {https://www.osti.gov/biblio/5572296}, journal = {J. Am. Chem. Soc.; (United States)},
number = ,
volume = 109:22,
place = {United States},
year = {Wed Oct 28 00:00:00 EST 1987},
month = {Wed Oct 28 00:00:00 EST 1987}
}