Li Zi-Sheng, Chen Wei-Xing, Morgan Harry W T, Shu Cong-Cong, McGrady John E, Sun Zhong-Ming
Department of Chemistry, University of Oxford South Parks Road Oxford OX1 3QR UK
State Key Laboratory of Elemento-Organic Chemistry, Tianjin Key Lab for Rare Earth Materials and Applications, School of Materials Science and Engineering, Nankai University Tianjin 300350 China
Chem Sci. 2023 Dec 2;15(3):1018-1026. doi: 10.1039/d3sc04709a. eCollection 2024 Jan 17.
The endohedral Zintl-ion cluster [FeSn] contains a linear Fe core with short Fe-Fe bond lengths of 2.4300(9) Å. The ground state is a septet, with significant σ and π contributions to the Fe-Fe bonds. The Sn cage is made up of two partially fused Sn fragments, and is structurally intermediate between [NiCdSn], where the fragments are clearly separated and [PdSn], where they are completely fused. It therefore represents an intermediate stage in cluster growth. Analysis of the electronic structure suggests that the presence of the linear Fe-Fe-Fe unit is an important factor in directing reactions towards fusion of the two Sn units rather than the alternative of oligomerization exo bond formation.
内嵌式津特耳离子簇[FeSn]包含一个线性铁核，铁-铁键长较短，为2.4300(9) Å。基态为七重态，对铁-铁键有显著的σ和π贡献。锡笼由两个部分融合的锡片段组成，其结构介于片段明显分离的[NiCdSn]和片段完全融合的[PdSn]之间。因此，它代表了簇生长的一个中间阶段。电子结构分析表明，线性Fe-Fe-Fe单元的存在是引导反应朝着两个锡单元融合而非形成外向键的低聚反应方向进行的一个重要因素。
