Electron-rich bioctahedral rhenium chalcohalide clusters [Re12CS14(mu-S)(3)Cl-6](8-) and [Re12CS14(mu-S)(3)Br-6](8-) : Synthesis, structure and properties

摘要

A first method for obtaining of electron-rich bioctahedral rhenium clusters has been developed. Two cluster salts, namely (Et3NH)(4)(Me2NH2)(4)[Re12CS14(mu-S)(3)Cl-6](1) and (Et4N)(4)(Me2NH2)(4)[Re12CS14(mu-S)(3)Br-6] (2), have been synthesized and isolated in the solid state. Single-crystal X-ray diffraction showed that salts 1 and 2 are based on the new cluster anions [Re12CS14(mu-S)(3)Cl-6](8-) and [Re12CS14(mu-S)(3)Br-6](8-) containing 48 cluster valence electrons (CVE). The correlations between geometry and CVE number of the bioctahedral chalcohalide anions have been examined using the DFT calculations. The dissolution of the salts 1 and 2 is accompanied by the oxidation yielding the [Re12CS14(mu-S)(3)Cl-6](6-) and [Re12CS14(mu-S)(3)Br-6](6-) anions. Properties of the new clusters in the DMSO solutions have been investigated by UV-Vis spectroscopy and cyclic voltammetry. The latter revealed the presence of multiple reversible one-electron redox waves in a narrow potential window. (C) 2018 Elsevier Ltd. All rights reserved.