Contrasting Solvent and Capping Ligand Effects Directing the Photochemistry of Uranyl(VI) Schiff Base Complexes

Photolysis of the uranyl(VI) Schiff base complex UO2( t Bu4-salphen)(THF) (1a) with cobaltocene in THF affords [Cp2Co][UO2( t Bu4-salphen)(OH)] (2) in high yield while irradiation in toluene yields no reaction. Electronic emission spectra of 1a reveal a large Stokes' shift in toluene similar to...

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Bibliographic Details
Published in:Journal of the American Chemical Society 2006-08, Vol.128 (33), p.10656-10657
Main Authors: Vaughn, Anthony E, Bassil, Daniel B, Barnes, Charles L, Tucker, Sheryl A, Duval, Paul B
Format: Article
Language:English
Subjects:
Chemistry
Exact sciences and technology
General and physical chemistry
Photochemistry
Physical chemistry of induced reactions (with radiations, particles and ultrasonics)
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Summary:Photolysis of the uranyl(VI) Schiff base complex UO2( t Bu4-salphen)(THF) (1a) with cobaltocene in THF affords [Cp2Co][UO2( t Bu4-salphen)(OH)] (2) in high yield while irradiation in toluene yields no reaction. Electronic emission spectra of 1a reveal a large Stokes' shift in toluene similar to that observed in the free ligand, while in THF the structural rearrangement responsible for this shift is blocked. Instead, the ligand-centered excited state is redirected to the uranyl(VI) center by way of energy transfer, thus generating 2 from the intramolecular activation of a coordinated THF molecule.
ISSN:0002-7863
1520-5126
DOI:10.1021/ja062735v