Facile direct insertion of nitrosonium ion (NO+) into a ruthenium-aryl bond

An insertion reaction of nitrosonium ion (NO+) into the metal−carbon bond of cyclometalated ruthenium(II) complexes is prepared with experimental evidence supporting a bimolecular direct NO+ insertion into the metal−carbon bond (i.e., M−R + NO+ → [M−N(═O)−R]+) but not an intramolecular migratory ins...

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Bibliographic Details
Main Authors: Pat, Pak-Kei, Lau, Tai-Chu, Wong, Chun-Yuen, Chan, Siu-Chung
Other Authors: School of Physical and Mathematical Sciences
Format: Journal Article
Language:English
Published: 2015
Subjects:
Online Access:https://hdl.handle.net/10356/107441
http://hdl.handle.net/10220/25490
Description
Summary:An insertion reaction of nitrosonium ion (NO+) into the metal−carbon bond of cyclometalated ruthenium(II) complexes is prepared with experimental evidence supporting a bimolecular direct NO+ insertion into the metal−carbon bond (i.e., M−R + NO+ → [M−N(═O)−R]+) but not an intramolecular migratory insertion (i.e., R−M−(NO) + L → L−M−N(═O)R) as the reaction mechanism. Theoretical calculations suggest that the direct NO+ insertion into the M−C bond may be rationalized as a frontier orbital interaction between the [Ru−aryl]-dominated HOMO of the Ru(II) complexes and the LUMO of the NO+.