Synthesis and Properties of Complexes of Vanadium(V) Oxide Trichloride with Nitrogen- and Oxygen-Donor Ligands

✍ Scribed by Charlotte D. Beard; Rosalind J. Barrie; John Evans; William Levason; Gillian Reid; Mark D. Spicer

• Publisher: John Wiley and Sons
• Year: 2006
• Tongue: English
• Weight: 154 KB
• Volume: 2006
• Category: Article
• ISSN: 1434-1948
• DOI: 10.1002/ejic.200600513

✦ Synopsis

Abstract

Intensely coloured, extremely moisture sensitive complexes [VOCl~3~(L)] (L = pyridine, quinoline, Ph~3~PO, Ph~3~AsO, pyridine N‐oxide), [VOCl~3~(L)~2~] (L = pyridine, Me~3~PO, pyridine N‐oxide), [VOCl~3~(L–L)] [L–L = 2,2′‐bipyridyl, 1,10‐phenanthroline, Ph~2~P(O)CH~2~P(O)Ph~2~, MeOCH~2~CH~2~OMe, 15‐crown‐5or Me~2~NCH~2~CH~2~NMe~2~] and [Cl~3~OV(μ‐L–L)VOCl~3~] [L–L =18‐crown‐6 or Ph~2~P(O)CH~2~P(O)Ph~2~] have been prepared from VOCl~3~ and the appropriate ligands in dichloromethane solution. These constitute the first extended series of complexes of vanadium(V) with neutral donor ligands. They have been fully characterised by analysis, IR, UV/Visible and multinuclear (^1^H, ^31^P, ^51^V) NMR spectroscopy, and their solution behaviour probed as a function of temperature using ^51^V NMR spectroscopy. Reducing ligands including phosphanes, arsanes, thio‐ and selenoethers immediately reduce VOCl~3~ to give V^IV^ or V^III^ species. Oxygen atom transfer reactions of some of the complexes with Ph~3~P, Ph~3~As, Me~2~Se and Bu~2~S, leading to the corresponding ligand oxides are also described. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006)