Schläfer Johannes, Tyrra Wieland, Mathur Sanjay
Institute of Inorganic Chemistry, University of Cologne , Greinstraße 6, D-50939 Cologne, Germany.
Inorg Chem. 2014 Mar 17;53(6):2751-3. doi: 10.1021/ic4025876. Epub 2014 Mar 3.
An advanced synthesis for the homometallic derivative [Ce2(O(t)Bu)8] (1) starting from [Ce(O(t)Bu)2{N(SiMe3)2}2] was developed. Structural characterization of a cerium(IV) complex and its decomposition products confirmed the coexistence of both ether elimination and Ce-O bond cleavage processes, which lead to the formation of [Ce3O(O(t)Bu)10] and [Ce3(O(t)Bu)11] (2) derivatives, respectively. Variable-temperature NMR spectroscopy under strict exclusion of moisture enabled insight into the decomposition processes in noncoordinating solvents and at elevated temperature. In addition, structural analysis of the heterovalent 2 and of two new complexes of the general formula [Ce2(O(t)Bu)8(L)] [L = HO(t)Bu (3), OCPh2 (4)] is described.
开发了一种从[Ce(O(t)Bu)2{N(SiMe3)2}2]出发合成同金属衍生物[Ce2(O(t)Bu)8] (1)的先进方法。对铈(IV)配合物及其分解产物的结构表征证实了醚消除和Ce - O键断裂过程的共存，这分别导致了[Ce3O(O(t)Bu)10]和[Ce3(O(t)Bu)11] (2)衍生物的形成。在严格排除水分的条件下进行变温核磁共振光谱分析，能够深入了解在非配位溶剂和高温下的分解过程。此外，还描述了异价配合物2以及通式为[Ce2(O(t)Bu)8(L)] [L = HO(t)Bu (3), OCPh2 (4)]的两种新配合物的结构分析。
