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1H, 13C and 15N NMR studies on adducts formation of rhodium(II) tetraacylates with some azoles in CDCl3 solution

✍ Scribed by Wojciech Bocian; Jarosław Jaźwiński; Agnieszka Sadlej

Publisher: John Wiley and Sons
Year: 2008
Tongue: English
Weight: 230 KB
Volume: 46
Category: Article
ISSN: 0749-1581
DOI: 10.1002/mrc.2149

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✦ Synopsis

Abstract

Adduct formations of rhodium(II) tetraacetate and tetratrifluoroacetate with some 1H‐imidazoles, oxazoles, thiazoles, 1H‐pyrazoles and isoxazole have been investigated by the use of ^1^H, ^13^C, ^15^N NMR and electronic absorption spectroscopy (VIS) in the visible range. Azoles tend to form axial adducts containing rhodium(II) tetraacylates bonded via nitrogen atom. Bulky substituents close to the nitrogen atom prevent the RhN bond formation, and in several cases switch over the binding site to the oxygen or sulphur atoms. The ^15^N adduct formation shift Δδ(^15^N) (Δδ = δ~adduct~ − δ~ligand~) varied from ca − 40 to − 70 ppm for the nitrogen atom involved in complexation, and of a few parts per million only, from ca − 6 to 3 ppm, for the non‐bonded nitrogen atom within the same molecule. The Δδ(^1^H) values do not exceed one ppm; Δδ(^13^C) ranges from − 1 to 6 ppm. Various complexation modes have been proved by electronic absorption spectroscopy in the visible region (VIS). For comparison purposes, some adducts of pyridine, thiophene and furan derivatives have been measured as well. The experimental findings were compared with calculated chemical shifts, obtained by means of DFT B3LYP method, using 6‐311 + G(2d,p), 6‐31(d)/LanL2DZ and 6‐311G(d,p) basis set. Copyright © 2007 John Wiley & Sons, Ltd.

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