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Reversing Conventional Reactivity of Mixed Oxo/Alkyl Rare‐Earth Complexes: Non‐Redox Oxygen Atom Transfer
Author(s) -
Hong Jianquan,
Tian Haiwen,
Zhang Lixin,
Zhou Xigeng,
del Rosal Iker,
Weng Linhong,
Maron Laurent
Publication year - 2018
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.201711305
Subject(s) - alkyl , reactivity (psychology) , chemistry , cluster (spacecraft) , redox , ligand (biochemistry) , rare earth , oxygen atom , metal , atom (system on chip) , oxygen , combinatorial chemistry , stereochemistry , molecule , photochemistry , inorganic chemistry , organic chemistry , medicine , biochemistry , mineralogy , alternative medicine , receptor , pathology , computer science , embedded system , programming language
The preferential substitution of oxo ligands over alkyl ones of rare‐earth complexes is commonly considered as “impossible” due to the high oxophilicity of metal centers. Now, it has been shown that simply assembling mixed methyl/oxo rare‐earth complexes to a rigid trinuclear cluster framework cannot only enhance the activity of the Ln‐oxo bond, but also protect the highly reactive Ln‐alkyl bond, thus providing a previously unrecognized opportunity to selectively manipulate the oxo ligand in the presence of numerous reactive functionalities. Such trimetallic cluster has proved to be a suitable platform for developing the unprecedented non‐redox rare‐earth‐mediated oxygen atom transfer from ketones to CS 2 and PhNCS. Controlled experiments and computational studies shed light on the driving force for these reactions, emphasizing the importance of the sterical accessibility and multimetallic effect of the cluster framework in promoting reversal of reactivity of rare‐earth oxo complexes.