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- Title
A Combined Experimental and Theoretical Study of the Versatile Reactivity of an Oxocerium(IV) Complex: Concerted Versus Reductive Addition.
- Authors
Castro, Ludovic; So, Yat‐Ming; Cho, Chang‐woo; Lortz, Rolf; Wong, Kai‐Hong; Wang, Kai; Arnold, Polly L.; Au‐Yeung, Ka‐Chun; Sung, Herman H.‐Y.; Williams, Ian D.; Leung, Wa‐Hung; Maron, Laurent
- Abstract
A combined experimental and theoretical investigation on the cerium(IV) oxo complex [(LOEt)2Ce(=O)(H2O)]⋅MeC(O)NH2 (1; LOEt−=[Co(η5‐C5H5){P(O)(OEt)2}3]−) demonstrates that the intermediate spin‐state nature of the ground state of the cerium complex is responsible for the versatility of its reactivity towards small molecules such as CO, CO2, SO2, and NO. CASSCF calculations together with magnetic susceptibility measurements indicate that the ground state of the cerium complex is of multiconfigurational character and comprised of 74 % of CeIV and 26 % of CeIII. The latter is found to be responsible for its reductive addition behavior towards CO, SO2, and NO. This is the first report to date on the influence of the multiconfigurational ground state on the reactivity of a metal–oxo complex.
- Subjects
MATHEMATICAL complexes; MAGNETIC susceptibility; MAGNETIC measurements; CERIUM; SMALL molecules; WATER
- Publication
Chemistry - A European Journal, 2019, Vol 25, Issue 46, p10834
- ISSN
0947-6539
- Publication type
Academic Journal
- DOI
10.1002/chem.201903035