Insititut des Sciences et Ingénierie Chimiques , Ecole Polytechnique Fédérale de Lausanne (EPFL) , 1015 Lausanne , Switzerland.
Laboratory for Quantum Magnetism, Institute of Physics , Ecole Polytechnique Fédérale de Lausanne (EPFL) , 1015 Lausanne , Switzerland.
J Am Chem Soc. 2019 Jun 26;141(25):9827-9831. doi: 10.1021/jacs.9b05337. Epub 2019 Jun 13.
Lanthanides (Ln) usually occur in the +3, or more recently the +2, oxidation states. The only example of an isolated molecular Ln so far remains Ce. Here we show that the +4 oxidation state is also accessible in a molecular compound of terbium as demonstrated by oxidation of the tetrakis(siloxide)terbium(III) ate complex, [KTb(OSi(O Bu))], 1-Tb, with the tris(4-bromophenyl)amminium oxidant, [N(CHBr)][SbCl], to afford the Tb complex [Tb(OSi(O Bu))], 2-Tb. The solid state structures of 1-Tb and 2-Tb were determined by X-ray crystallography, and the presence of Tb was unambiguously confirmed by electron paramagnetic resonance and magnetometry. Complex 2-Tb displays a similar voltammogram to the Ce analogue but with redox events that are about 1 V more positive.
镧系元素（Ln）通常以+3 价存在，或者最近以+2 价存在。到目前为止，唯一分离的分子镧系元素的例子仍然是铈。在这里，我们表明+4 氧化态也可以在三价四硅氧烷合铽（III）烷氧根配合物[KTb（OSi（O Bu））]，1-Tb 的分子化合物中获得，该配合物用三（4-溴苯基）氨盐氧化剂[N（CHBr）][SbCl]氧化，得到铽配合物[Tb（OSi（O Bu））]，2-Tb。通过 X 射线晶体学确定了 1-Tb 和 2-Tb 的固体结构，并通过电子顺磁共振和磁强计明确证实了铽的存在。配合物 2-Tb 显示出与 Ce 类似物相似的循环伏安图，但氧化还原事件的电位约正 1 V。
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