Electron-rich bioctahedral rhenium chalcohalide clusters [Re12CS14(µ-S)3Cl6]8− and [Re12CS14(µ-S)3Br6]8−: Synthesis, structure and properties. (1st September 2018)

• Record Type: Journal Article
• Authors: Gayfulin, Yakov M.; Ryzhikov, Maxim R.; Samsonenko, Denis G.; Mironov, Yuri V.
• Is Part Of: Polyhedron. Volume 151(2018)
• Page Start: 426
• Page End: 432
• Publication Date: 2018-09-01
• Subjects: Rhenium -- Cluster compound -- Crystal structure -- DFT calculations -- Redox properties; Chemistry, Inorganic -- Periodicals; Chimie inorganique -- Périodiques; Organometaalverbindingen; Anorganische chemie; 546.05
• DOI: 10.1016/j.poly.2018.05.061
• Languages: English
• ISSNs: 0277-5387

Abstract

Graphical abstract: Electron-rich bioctahedral rhenium chalcohalide clusters [Re12 CS14 (µ-S)3 Cl6 ] 8− and [Re12 CS14 (µ-S)3 Br6 ] 8− were synthesized and isolated in solid state. Single crystal X-ray structure, electronic structure calculations and redox properties of the new clusters are reported. Abstract: A first method for obtaining of electron-rich bioctahedral rhenium clusters has been developed. Two cluster salts, namely (Et3 NH)4 (Me2 NH2 )4 [Re12 CS14 (µ-S)3 Cl6 ] (1 ) and (Et4 N)4 (Me2 NH2 )4 [Re12 CS14 (µ-S)3 Br6 ] (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 [Re12 CS14 (µ-S)3 Cl6 ] 8− and [Re12 CS14 (µ-S)3 Br6 ] 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 [Re12 CS14 (µ-S)3 Cl6 ] 6− and [Re12 CS14 (µ-S)3 Br6 ] 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.