Variation of electronic transitions and reduction potentials of cerium(IV) complexes.
Variation of electronic transitions and reduction potentials of cerium(IV) complexes.
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DOI：
10.1039/c4dt01386g
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发表时间：
2014-10
影响因子：
4
通讯作者：
U. Williams;David Schneider;Walter L. Dorfner;Cäcilia Maichle-Mössmer;P. Carroll;R. Anwander;E. Schelter
中科院分区：
文献类型：
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作者：
U. Williams;David Schneider;Walter L. Dorfner;Cäcilia Maichle-Mössmer;P. Carroll;R. Anwander;E. Schelter
合成了三价化合物K[Ce[N（SiHMe 2）2]4]，并将其氧化，为合成铈（IV）化合物Ce[N（SiHMe 2）2]4提供了一条方便的途径。Ce[N（SiHMe 2）2]4与叔丁醇、取代苯甲醇和2，6-二苯基苯酚发生质子分解反应，得到中性四价化合物Ce（O（t）Bu）4（py）2、Ce 2（OCH 2C 6 R5）8（thf）2（R = Me，F）和Ce（Odpp）4（dpp = 2，6-（C6 H5）2-C6 H3）。光谱和电化学表征的monoclonal铈（IV）甲硅烷基酰胺，醇盐，和芳氧基化合物显示变量配体到金属的电荷转移跃迁和金属为基础的还原电位。进行计算键合分析，以补充复合物的物理特性。
The trivalent compound K[Ce[N(SiHMe2)2]4] was synthesized and oxidized, providing a convenient route to the reported cerium(IV) compound Ce[N(SiHMe2)2]4. Protonolysis reactions of Ce[N(SiHMe2)2]4 with tert-butanol, substituted benzyl alcohols, and 2,6-diphenylphenol yielded the neutral tetravalent compounds Ce(O(t)Bu)4(py)2, Ce2(OCH2C6R5)8(thf)2 (R = Me, F), and Ce(Odpp)4 (dpp = 2,6-(C6H5)2-C6H3). Spectroscopic and electrochemical characterization of the monometallic cerium(IV) silylamide, alkoxide, and aryloxide compounds revealed variable ligand-to-metal charge transfer transitions and metal-based reduction potentials. Computational bonding analyses were performed to complement the physical characterization of the complexes.