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Combining Solid-state and Solution-based Techniques: Synthesis and Reactivity of ChalcogenidoplumbatesII or IV
Published on: December 29, 2016
Cerium(IV) Phosphido Complexes
Ning Wang1, Xiaoyu Li2, Hui Guo3
1Spin-X Institute, School of Chemistry and Chemical Engineering, State Key Laboratory of Luminescent Materials and Devices, South China University of Technology, Guangzhou 510641, China.
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Although the development of tetravalent lanthanide complexes has accelerated recently, it still lags far behind that of their trivalent congeners. Herein, we report the synthesis and structural characterization of the first tetravalent lanthanide phosphido complexes, [(ImtBuN)3CeIVP(SiMe3)Ar] (Ar = C6H5 (1), C6H3-2,6-iPr2 (2)). Single-crystal X-ray diffraction reveals a pyramidal geometry around the phosphorus atom in 1, whereas a trigonal planar geometry and a shorter Ce-P distance in 2 suggest the presence of a Ce-P π-interaction alongside the σ-bond. Computational studies corroborate these findings, revealing polarized Ce-P bonds with significant double-bond character. Notably, f-orbital contributions are substantial for both σ-type (28-51%) and π-type (67%) bonding interactions. Preliminary reactivity studies demonstrate that complex 1 undergoes addition reactions with AdN3 and Ph2CN2, rather than redox processes.
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