Anhydrous photochemical uranyl(VI) reduction: unprecedented retention of equatorial coordination accompanying reversible axial oxo/alkoxide exchange

Shanmugaperumal Kannan; Anthony E Vaughn; Eric M Weis; Charles L Barnes; Paul B Duval

doi:10.1021/ja065822w

Anhydrous photochemical uranyl(VI) reduction: unprecedented retention of equatorial coordination accompanying reversible axial oxo/alkoxide exchange

J Am Chem Soc. 2006 Nov 1;128(43):14024-5. doi: 10.1021/ja065822w.

Authors

Shanmugaperumal Kannan¹, Anthony E Vaughn, Eric M Weis, Charles L Barnes, Paul B Duval

Affiliation

¹ Department of Chemistry, University of Missouri-Columbia, 601 South College Avenue, Columbia, MO 65211, USA.

PMID: 17061874
DOI: 10.1021/ja065822w

Abstract

In a dramatic reversal of the normal trend of observed reactivity in uranyl(VI) coordination chemistry, an unprecedented retention of the normally labile equatorial coordination plane accompanies facile and reversible axial oxo/alkoxide exchange during both the photochemical reduction of cationic uranyl(VI) phosphine-oxide complexes with organic substrates and subsequent hydrolysis of the uranium(IV) alkoxide complexes to regenerate the uranyl(VI) starting complex.