Kinetics and mechanism of a macrocyclic chromium(III) complex oxidation to chromium(IV) by hexacyanoferrate(III) in strongly alkaline media

J. Chatlas, O. Impert, A. Katafias, P. Kita, G. Wrzeszcz, J. Eriksen, O. Monsted, Andrew Mills

Research output: Contribution to journalArticlepeer-review

10 Citations (Scopus)

Abstract

Oxidation of the macrocyclic Cr(III) complex cis-[Cr(cycb)(OH)(2)](+), where cycb = rac-5,5,7,12,12,14-hexamethyl-1,4,8,11-tetraazacyclotetradecane, by an excess of the hexacyanoferrate( III) in basic solution, slowly produces Cr(V) species. These species, detected using e.p.r. spectroscopy, are stable under ambient conditions for many hours, and the hyperfine structure of the e.p.r. spectrum is consistent with the interaction of the d-electron with four equivalent nitrogen nuclei. Electro-spray ionization mass spectrometry suggests a concomitant oxidation of the macrocyclic ligand, in which double bonds and double bonded oxygen atoms have been introduced. By comparison basic chromate(III) solutions are oxidized rapidly to chromate(VI) by hexacyanoferrate(III) without any detectable generation of stable Cr(V) intermediates.
Original languageEnglish
Pages (from-to)634-643
Number of pages10
JournalTransition Metal Chemistry
Volume29
Issue number6
Publication statusPublished - Sep 2004

ASJC Scopus subject areas

  • Inorganic Chemistry

Fingerprint Dive into the research topics of 'Kinetics and mechanism of a macrocyclic chromium(III) complex oxidation to chromium(IV) by hexacyanoferrate(III) in strongly alkaline media'. Together they form a unique fingerprint.

Cite this