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A Combined Experimental and Theoretical Study of the Versatile Reactivity of an Oxocerium(IV) Complex: Concerted Versus Reductive Addition
Author(s) -
Castro Ludovic,
So YatMing,
Cho Changwoo,
Lortz Rolf,
Wong KaiHong,
Wang Kai,
Arnold Polly L.,
AuYeung KaChun,
Sung Herman H.Y.,
Williams Ian D.,
Leung WaHung,
Maron Laurent
Publication year - 2019
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201903035
Subject(s) - reactivity (psychology) , cerium , ground state , chemistry , metal , molecule , computational chemistry , photochemistry , medicinal chemistry , inorganic chemistry , atomic physics , physics , organic chemistry , medicine , alternative medicine , pathology
A combined experimental and theoretical investigation on the cerium(IV) oxo complex [(L OEt ) 2 Ce(=O)(H 2 O)] ⋅ MeC(O)NH 2 ( 1 ; L OEt − =[Co(η 5 ‐C 5 H 5 ){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, CO 2 , SO 2 , 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, SO 2 , 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.