Williams Ursula J, Schneider David, Dorfner Walter L, Maichle-Mössmer Cäcilia, Carroll Patrick J, Anwander Reiner, Schelter Eric J
P. Roy and Diana T. Vagelos Laboratories, Department of Chemistry, University of Pennsylvania, 231 South 34th Street, Philadelphia, Pennsylvania 19104, USA.
Dalton Trans. 2014 Nov 21;43(43):16197-206. doi: 10.1039/c4dt01386g.
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.
合成并氧化了三价化合物K[Ce[N(SiHMe2)2]4]，为已报道的铈(IV)化合物Ce[N(SiHMe2)2]4提供了一条便捷的合成路线。Ce[N(SiHMe2)2]4与叔丁醇、取代苄醇和2,6-二苯基苯酚发生质子解反应，生成了中性四价化合物Ce(O(t)Bu)4(py)2、Ce2(OCH2C6R5)8(thf)2（R = Me，F）和Ce(Odpp)4（dpp = 2,6-(C6H5)2-C6H3）。对单金属铈(IV)硅烷基酰胺、醇盐和芳氧基化合物进行的光谱和电化学表征揭示了不同的配体到金属的电荷转移跃迁和基于金属的还原电位。进行了计算键合分析以补充配合物的物理表征。
