201. A Combined Experimental and Theoretical Study of the Versatile Reactivity of an Oxocerium(IV) Complex: Concerted Versus Reductive Addition
- Author
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Wa-Hung Leung, Kai Wang, Ludovic Castro, Yat-Ming So, Ka Chun Au-yeung, Kai-Hong Wong, Polly L. Arnold, Herman H. Y. Sung, Ian D. Williams, Chang-woo Cho, Rolf Lortz, Laurent Maron, Laboratoire de physique et chimie des nano-objets (LPCNO), Institut National des Sciences Appliquées - Toulouse (INSA Toulouse), Institut National des Sciences Appliquées (INSA)-Université de Toulouse (UT)-Institut National des Sciences Appliquées (INSA)-Université de Toulouse (UT)-Institut de Chimie de Toulouse (ICT), Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Université de Toulouse (UT)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-Institut de Recherche sur les Systèmes Atomiques et Moléculaires Complexes (IRSAMC), Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Université de Toulouse (UT)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS), Department of Chemistry The Hong Kong University of Science and Technology, Edinburgh Napier University, University of Edinburgh, Hong Kong Research Grants Council [16300917], Royal Society of Chemistry for the Researcher Mobility Grant, EPSRC-UK [EP/N022122/1, EP/M010554/1], and China Scholarship Council
- Subjects
010405 organic chemistry ,ab initio calculations ,1,2-insertion ,cerium ,multiconfigurational ground state ,reductive insertion ,Organic Chemistry ,chemistry.chemical_element ,General Chemistry ,010402 general chemistry ,01 natural sciences ,Small molecule ,Magnetic susceptibility ,Catalysis ,0104 chemical sciences ,Cerium ,Crystallography ,Character (mathematics) ,chemistry ,Ab initio quantum chemistry methods ,Reactivity (chemistry) ,[PHYS.PHYS.PHYS-CHEM-PH]Physics [physics]/Physics [physics]/Chemical Physics [physics.chem-ph] ,Ground state - Abstract
International audience; A combined experimental and theoretical investigation on the cerium(IV) oxo complex [(L-OEt)(2)Ce(=O)(H2O)].MeC(O)NH2 (1; L-OEt(-)=[Co(eta(5)-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 Ce-IV and 26 % of Ce-III. 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.
- Published
- 2019
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