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Electron-rich bioctahedral rhenium chalcohalide clusters [Re12CS14(µ-S)3Cl6]8- and [Re12CS14(µ-S)3Br6]8-: Synthesis, structure and properties. / Gayfulin, Yakov M.; Ryzhikov, Maxim R.; Samsonenko, Denis G. и др.
в: Polyhedron, Том 151, 01.09.2018, стр. 426-432.Результаты исследований: Научные публикации в периодических изданиях › статья › Рецензирование
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TY - JOUR
T1 - Electron-rich bioctahedral rhenium chalcohalide clusters [Re12CS14(µ-S)3Cl6]8- and [Re12CS14(µ-S)3Br6]8-: Synthesis, structure and properties
AU - Gayfulin, Yakov M.
AU - Ryzhikov, Maxim R.
AU - Samsonenko, Denis G.
AU - Mironov, Yuri V.
N1 - Publisher Copyright: © 2018 Elsevier Ltd
PY - 2018/9/1
Y1 - 2018/9/1
N2 - A first method for obtaining of electron-rich bioctahedral rhenium clusters has been developed. Two cluster salts, namely (Et3NH)4(Me2NH2)4[Re12CS14(µ-S)3Cl6] (1) and (Et4N)4(Me2NH2)4[Re12CS14(µ-S)3Br6] (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(µ-S)3Cl6]8− and [Re12CS14(µ-S)3Br6]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(µ-S)3Cl6]6− and [Re12CS14(µ-S)3Br6]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.
AB - A first method for obtaining of electron-rich bioctahedral rhenium clusters has been developed. Two cluster salts, namely (Et3NH)4(Me2NH2)4[Re12CS14(µ-S)3Cl6] (1) and (Et4N)4(Me2NH2)4[Re12CS14(µ-S)3Br6] (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(µ-S)3Cl6]8− and [Re12CS14(µ-S)3Br6]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(µ-S)3Cl6]6− and [Re12CS14(µ-S)3Br6]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.
KW - Cluster compound
KW - Crystal structure
KW - DFT calculations
KW - Redox properties
KW - Rhenium
KW - POLYMERS
KW - LIGANDS
KW - MOLYBDENUM
KW - COMPLEXES
KW - METAL
KW - FRAMEWORKS
UR - http://www.scopus.com/inward/record.url?scp=85048784870&partnerID=8YFLogxK
U2 - 10.1016/j.poly.2018.05.061
DO - 10.1016/j.poly.2018.05.061
M3 - Article
AN - SCOPUS:85048784870
VL - 151
SP - 426
EP - 432
JO - Polyhedron
JF - Polyhedron
SN - 0277-5387
ER -
ID: 14101547