Ru-II complexes incorporating tetrathiamacrocycles: Synthesis and conformational analysis
authors Adams, H; Amado, AM; Felix, V; Mann, BE; Antelo-Martinez, J; Newell, M; Ribeiro-Claro, PJA; Spey, SE; Thomas, JA
nationality International
journal CHEMISTRY-A EUROPEAN JOURNAL
author keywords fluxionality; invertomers; macrocylic ligands; ruthenium; sulfur
keywords EFFECTIVE CORE POTENTIALS; THIOETHER MACROCYCLIC COMPLEXES; CAMBRIDGE STRUCTURAL DATABASE; ELECTRON-TRANSFER; MIXED-VALENCE; CRYSTAL-STRUCTURES; MOLECULAR CALCULATIONS; = 1,4,8,11-TETRATHIACYCLOTETRADECANE; RUTHENIUM(II) COMPLEXES; BINUCLEAR COMPLEXES
abstract The synthesis of a series of Ru-II complexes incorporating thiacrown ligands ([12]ane-S-4, [14]ane-S-4, [16]ane-S-4), 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 H-1 NMR spectroscopic studies on the previously reported [Ru([12]ane-S-4)(bpy)](2+) (1) reveal that-contrary to earlier reports-the observed fluxional H-1 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-S-4 and [16]ane-S-4 analogues of 1. For the first time, using a combination of X-ray crystallography, more detailed H-1 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]aneS(4))(bpy)](2+) complexes are determined by steric rather than electronic effects.
publisher WILEY-V C H VERLAG GMBH
issn 0947-6539
year published 2005
volume 11
issue 7
beginning page 2031
ending page 2046
digital object identifier (doi) 10.1002/chem.200400693
web of science category Chemistry, Multidisciplinary
subject category Chemistry
unique article identifier WOS:000227933800007
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