Structure and Bonding in [Sb@In8Sb12]3- and [Sb@In8Sb12]5-
Chao Liu, Nikolay V. Tkachenko, Ivan A. Popov, Nikita Fedik, Xue Min, Cong-Qiao Xu, Jun Li, John E. McGrady, Alexander I. Boldyrev, Zhong-Ming Sun*
Angew. Chem. Int. Ed. 2019, 58, 1-6 [ pdf ]
Chao Liu, Nikolay V. Tkachenko, Ivan A. Popov, Nikita Fedik, Xue Min, Cong-Qiao Xu, Jun Li, John E. McGrady, Alexander I. Boldyrev, Zhong-Ming Sun*
Angew. Chem. Int. Ed. 2019, 58, 1-6 [ pdf ]
Abstract： We report the characterization of the compound [K([2.2.2]crypt)]4[In8Sb13], which proves to contain a 1:1 mixture of [Sb@In8Sb12]3− and [Sb@In8Sb12]5−. The tri‐anion displays perfect Th symmetry, the first completely inorganic molecule to do so, and contains eight equivalent In3+ centers in a cube. The gas‐phase potential energy surface of the penta‐anion has eight equivalent minima where the extra pair of electrons is localized on one In+ center, and these minima are linked by low‐lying transition states where the electron pair is delocalized over two adjacent centers. The best fit to the electron density is obtained from a model where the structure of the 5− cluster lies close to the gas‐phase transition state.