A Combined Experimental and Theoretical Study of the Versatile Reactivity of an Oxocerium(IV) Complex: Concerted Versus Reductive Addition - INSA Toulouse - Institut National des Sciences Appliquées de Toulouse Access content directly
Journal Articles Chemistry - A European Journal Year : 2019

A Combined Experimental and Theoretical Study of the Versatile Reactivity of an Oxocerium(IV) Complex: Concerted Versus Reductive Addition

Abstract

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.
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Dates and versions

hal-04022190 , version 1 (09-03-2023)

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Ludovic Castro, Yat-Ming So, Chang-Woo Cho, Rolf Lortz, Kai-Hong Wong, et al.. A Combined Experimental and Theoretical Study of the Versatile Reactivity of an Oxocerium(IV) Complex: Concerted Versus Reductive Addition. Chemistry - A European Journal, 2019, 25 (46), pp.10834-10839. ⟨10.1002/chem.201903035⟩. ⟨hal-04022190⟩
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