Author: ["Yuri Tulchinsky","Mark A. Iron","Mark Botoshansky","Mark Gandelman"]
CITE.CC academic search helps you expand the influence of your papers.
Abstract
Unlike N-heterocyclic carbenes (NHCs), which are now used ubiquitously in metal-based chemistry, the nitrogen-derived analogue (in which a carbon is replaced with the isoelectronic nitrogen cation, a nitrenium ion) has remained elusive as a ligand for metals. This is especially intriguing, because several other main-group analogues of NHCs have been prepared, and have been shown to coordinate with transition-metal complexes. Here, we describe the preparation of several N-heterocyclic nitrenium ions that are isoelectronic and isostructural to NHCs, and study their ligand properties. The formation of relatively strong nitrenium–metal bonds is unambiguously confirmed, in solution by selective 15N-labelling experiments, and in the solid state by X-ray crystallography. Experimental and computational studies of the electronic properties of this novel type of ligand suggest that they are poor σ-donors and good π-acceptors. Nitrenium salts have been known for more than 100 years. Despite being isoelectronic and isostructural to the ubiquitous N-heterocyclic carbene ligands and other main-group analogues, their coordination to metals has remained elusive. Here, the first examples of nitrenium ions as ligands for transition metals are described, along with investigations of their electronic properties.Cite this article
Tulchinsky, Y., Iron, M., Botoshansky, M. et al. Nitrenium ions as ligands for transition metals. Nature Chem 3, 525–531 (2011). https://doi.org/10.1038/nchem.1068 