Premium
Coordination and Redox Isomerization in the Reduction of a Uranium(III) Monoarene Complex
Author(s) -
La Pierre Henry S.,
Kameo Hajime,
Halter Dominik P.,
Heinemann Frank W.,
Meyer Karsten
Publication year - 2014
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.201402048
Subject(s) - chemistry , isomerization , redox , cyclic voltammetry , ligand (biochemistry) , uranium , hydride , coordination complex , inorganic chemistry , stoichiometry , crown ether , divalent , uranyl , electrochemistry , ether , medicinal chemistry , photochemistry , metal , organic chemistry , ion , materials science , catalysis , electrode , biochemistry , receptor , metallurgy
Synthetic studies on the redox chemistry of trivalent uranium monoarene complexes were undertaken with a complex derived from the chelating tris(aryloxide)arene ligand ( Ad,Me ArO) 3 mes 3− . Cyclic voltammetry of [{( Ad,Me ArO) 3 mes}U III ] ( 1 ) revealed a nearly reversible and chemically accessible reduction at −2.495 V vs. Fc/Fc + —the first electrochemical evidence for a formally divalent uranium complex. Chemical reduction of 1 indicates that reduction induces coordination and redox isomerization to form a uranium(IV) hydride, and addition of a crown ether results in hydride insertion into the coordinated arene to afford uranium(IV) complexes. This stoichiometric reaction sequence provides structural insight into the mechanism of arene functionalization at diuranium inverted sandwich complexes.