RuII complexes incorporating tetrathiamacrocycles: synthesis and conformational analysis |
| |
Authors: | Adams Harry Amado A M Félix Vitor Mann Brian E Antelo-Martinez Jorge Newell Mike Ribeiro-Claro Paulo J A Spey Sharon E Thomas James A |
| |
Institution: | Department of Chemistry, University of Sheffield, Sheffield, S3 7HF, UK. |
| |
Abstract: | The synthesis of a series of RuII complexes incorporating thiacrown ligands (12]ane-S4, 14]ane-S4, 16]ane-S4), as well as 2,2'-bipyridine (bpy) or pyridine, is reported. Structural studies on these complexes have been carried out using a variety of techniques. Detailed 1H NMR spectroscopic studies on the previously reported Ru(12]ane-S4)(bpy)]2+ (1) reveal that-contrary to earlier reports-the observed fluxional 1H NMR behavior is not due to chemical exchange involving cleavage of the bpy Ru--N bond but is, in fact, due to lone-pair inversion of coordinated macrocyclic sulfur donor atoms. This phenomenon is also observed for the 14]ane-S4 and 16]ane-S4 analogues of 1. For the first time, using a combination of X-ray crystallography, more detailed 1H NMR experiments, and computational methods, an in-depth study on the energetics and dynamics of invertomer formation and conversion for macrocyclic coordination complexes has been carried out. These studies reveal that the steric constraints of assembling each sulfur macrocycle and bpy ligand around the octahedral Ru(II) center lead to close intramolecular contacts. These contacts are largely dependent on the orientation of the electron lone pairs of equatorial sulfur donor atoms and correlate with the comparative stability of the different invertomeric forms. Thus, the conformational preferences of the three macrocyles in Ru(n]ane-S4)(bpy)]2+ complexes are determined by steric rather than electronic effects. |
| |
Keywords: | fluxionality invertomers macrocylic ligands ruthenium sulfur |
本文献已被 PubMed 等数据库收录! |
|