Beuthert Katrin, Weinert Bastian, Wilson Robert J, Weigend Florian, Dehnen Stefanie
Fachbereich Chemie and Wissenschaftliches Zentrum für Materialwissenschaften (WZMW), Philipps-Universität Marburg, Hans-Meerwein-Strasse 4, 35043 Marburg, Germany.
Inorg Chem. 2023 Feb 6;62(5):1885-1890. doi: 10.1021/acs.inorgchem.2c01298. Epub 2022 May 31.
The impact of 4f metal ions Ln (Ln = La or Ce) versus 5f metal ions U ( = 3 or 4) on the compositions and distribution of 5p metal atoms in the cluster shells of endohedral species [M@SnSb] (M = La, Ce, or U; = 6-8; = 3, 4) was studied by means of combined experimental and quantum chemical investigations. While all known f-block metal ion-centered endohedral clusters possessed combinations of larger main group metal atoms so far (Sn/Bi or Pb/Bi), resulting in mixtures of 13- and 14-atom cages, the 14-atom cages reported herein comprise exclusively Sn and Sb atoms and therefore are challenged in accommodating the large 4f and 5f ions. We show that the clusters form in reactions of (SnSb) anions with [Ln(CMeH)] or [U(CMeH)Cl], and that salts of [La@SnSb], [La@SnSb], [U@SnSb], and [U@SnSb] can be isolated from them. The assignment of Sn versus Sb in the encapsulating cage follows a simple rule. Different central atoms cause only slight differences in this regard and with respect to distortions of the cluster shells. The reactions also yielded the salt of the new binary anion (SnSb) that was recently predicted by quantum chemical studies.
通过结合实验和量子化学研究，研究了4f金属离子Ln（Ln = La或Ce）与5f金属离子U（ = 3或4）对内嵌物种[M@SnSb]（M = La、Ce或U； = 6 - 8； = 3、4）簇壳中5p金属原子组成和分布的影响。虽然到目前为止所有已知的以f族金属离子为中心的内嵌簇都具有较大主族金属原子的组合（Sn/Bi或Pb/Bi），从而导致13原子和14原子笼的混合，但本文报道的14原子笼仅由Sn和Sb原子组成，因此在容纳大的4f和5f离子方面面临挑战。我们表明，这些簇在（SnSb）阴离子与[Ln（CMeH）]或[U（CMeH）Cl]的反应中形成，并且可以从中分离出[La@SnSb]、[La@SnSb]、[U@SnSb]和[U@SnSb]的盐。封装笼中Sn与Sb的归属遵循一个简单规则。不同的中心原子在这方面以及簇壳的扭曲方面仅引起轻微差异。这些反应还生成了最近量子化学研究预测的新二元阴离子（SnSb）的盐。
