作者:Jochen Friedrich、Yusen Qiao、Cäcilia Maichle-Mössmer、Eric J. Schelter、Reiner Anwander
DOI:10.1039/c8dt01878b
日期:——
by the siloxy ligand is evident, significant extra stabilization is gained if the siloxy ligand coordinates in a chelating fashion, which is further supported by DFT calculations. Natural bond orbital (NBO) analysis indicates an enhanced donation of the siloxy ligand electron density into the unfilled CeIV 6s, 4f, and 5d orbitals. CeIV to CeIII reduction readily occurs when homoleptic complex Ce[OSi(OtBu)3]4
通过电化学和计算方法以及有针对性的氧化还原化学揭示了三(叔丁氧基)甲硅烷氧基配体对铈(IV)的稳定作用。Ce [OSi(O t Bu)3 ] 4可通过在室温下于乙腈中使[Et 4 N] 2 [ CeCl 6 ]与NaOSi(O t Bu)3反应而获得Ce [OSi(O t Bu)3 ] 4。 [Ce OSi(O t Bu)3 } 4 ] [K(2.2.2-crypt)]易于从[Ce OSi(O t Bu)3 } 4合成。K]和cryptand。的固态结构monocerium络合物铈[OSi的(O吨丁基)3 ] 4和Ce [OSi的(O吨丁基)3 ] 4(THF)显示5-和6-配位的Ce IV中心(一个κ 2键合的甲硅烷氧基配体),而复杂的[Ce OSi(O t Bu)3 } 4 ] [K(2.2.2-crypt)]则显示4坐标的Ce III中心(全末端甲硅烷氧基配位)。Ce [OSi(O