Oxygen atom exchange reaction between tetradentate Schiff base-oxovanadium(IV) complexes and water

Masanobu Tsuchimoto, Gakuse Hoshina, Ryushi Uemura, Kiyohiko Nakajima, Masaaki Kojima, Shigeru Ohba

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Abstract

The oxygen atom exchange reaction between the terminal oxygen atom (V=O) of tetradentate Schiff base-oxovanadium(IV) complexes and water slowly proceeds in DMSO solutions. The rate constants k(obs) for the isotopic oxygen atom exchange reaction in DMSO solutions containing excess H 2 18O at 50 °C under an argon atmosphere were obtained for several complexes (6 x 10 -7 to 6 x 10 -5 s -1). The reaction proceeds faster for those complexes with electron-withdrawing groups at the Schiff base ligand moieties, and slower for the complexes with bulky hydrophobic groups. The oxygen atom exchange reaction and isomerization reaction under an argon atmosphere and in air were investigated for oxovanadium(IV) complexes that have two geometrical isomers. Water molecules attack the vanadium atom mainly from the same side of the oxo ligand for the oxovanadium(IV) complexes, whereas mainly from the opposite side of the oxo ligand for the oxovanadium(V) complexes produced by oxidation with air.

Original languageEnglish
Pages (from-to)2317-2323
Number of pages7
JournalBulletin of the Chemical Society of Japan
Volume73
Issue number10
DOIs
Publication statusPublished - 2000 Oct 1

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ASJC Scopus subject areas

  • Chemistry(all)

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