Reversing Conventional Reactivity of Mixed Oxo/Alkyl Rare‐Earth Complexes: Non‐Redox Oxygen Atom Transfer |
| |
Authors: | Dr Jianquan Hong Haiwen Tian Prof Lixin Zhang Prof Xigeng Zhou Dr Iker del?Rosal Prof Linhong Weng Prof Laurent Maron |
| |
Institution: | 1. Department of Chemistry, Shanghai Key Laboratory of Molecular Catalysis and Innovative Materials, Fudan University, Shanghai, P. R. China;2. State Key Laboratory of Organometallic Chemistry, Shanghai, P. R. China;3. LPCNO, Université de Toulouse, Toulouse, France |
| |
Abstract: | 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 CS2 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. |
| |
Keywords: | cluster compounds organometallic chemistry oxygen atom transfer rare-earth complexes theoretical chemistry |
|
|