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Is the bipyridyl thorium metallocene a low-valent thorium complex? A combined experimental and computational study [electronic resource].

Published:
Washington, D.C. : United States. Dept. of Energy. Office of Science, 2012.
Oak Ridge, Tenn. : Distributed by the Office of Scientific and Technical Information, U.S. Dept. of Energy.
Physical Description:
11 : digital, PDF file
Additional Creators:
Lawrence Berkeley National Laboratory, United States. Department of Energy. Office of Science, and United States. Department of Energy. Office of Scientific and Technical Information
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Summary:
Bipyridyl thorium metallocenes [5-1,2,4-(Me3C)3C5H2]2Th(bipy) (1) and [5-1,3-(Me3C)2C5H3]2Th(bipy) (2) have been investigated by magnetic susceptibility and computational studies. The magnetic susceptibility data reveal that 1 and 2 are not diamagnetic, but they behave as temperature independent paramagnets (TIPs). To rationalize this observation, density functional theory (DFT) and complete active space SCF (CASSCF) calculations have been undertaken, which indicated that Cp2Th(bipy) has indeed a Th(IV)(bipy2-) ground state (f0d0 2, S = 0), but the open-shell singlet (f0d1 1, S = 0) (almost degenerate with its triplet congener) is lying only 9.2 kcal/mol higher in energy. Complexes 1 and 2 react cleanly with Ph2CS to give [ 5-1,2,4-(Me3C)3C5H2]2Th[(bipy)(SCPh2)] (3) and [ 5-1,3-(Me3C)2C5H3]2Th[(bipy)(SCPh2)] (4), respectively, in quantitative conversions. Since no intermediates were observed experimentally, this reaction was also studied computationally. Coordination of Ph2CS to 2 in its S = 0 ground state is not possible, but Ph2CS can coordinate to 2 in its triplet state (S = 1) upon which a single electron transfer (SET) from the (bipy2-) fragment to Ph2CS followed by C-C coupling takes place.
Report Numbers:
E 1.99:lbnl-6716e
lbnl-6716e
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Note:
Published through SciTech Connect.
01/12/2012.
"lbnl-6716e"
Chemical Science FT
Maron, Laurent; Zi, Guofu; Lukens, Wayne W.; Walter, Marc D.; Ren, Wenshan.
Funding Information:
DE-AC02-05CH11231
View MARC record | catkey: 14392269