Affiliation:
1. Department of Chemistry and Biochemistry, University of California, San Diego, 9500 Gilman Drive, MC 0358, La Jolla, CA 92093, USA.
Abstract
The electron-rich, six-coordinate tris-aryloxide uranium(III) complex [((
Ad
ArO)
3
tacn)U
III
] [where (
Ad
ArOH)
3
tacn = 1,4,7-tris(3-adamantyl-5-
tert
-butyl-2-hydroxybenzyl)1,4,7-triazacyclononane] reacts rapidly with CO
2
to yield [((
Ad
ArO)
3
tacn)U
IV
(CO
2
)], a complex in which the CO
2
ligand is linearly coordinated to the metal through its oxygen atom (η
1
-OCO). The latter complex has been crystallographically and spectroscopically characterized. The inequivalent O–C–O bond lengths [1.122 angstroms (Å) for the O–C bond adjacent to uranium and 1.277 Å for the other], considered together with magnetization data and electronic and vibrational spectra, support the following bonding model: U
IV
=O=C⚫–O
–
↔ U
IV
–O
C–O
–
. In these charge-separated resonance structures, the uranium center is oxidized to uranium(IV) and the CO
2
ligand reduced by one electron.
Publisher
American Association for the Advancement of Science (AAAS)
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