Abstract
Attempts to prepare the hitherto unknown Se6 2+ cation by the reaction of elemental selenium and Ag[A] ([A]- = [Sb(OTeF5)6]-, [Al(OC(CF3)3)4]-) in SO2 led to the formation of [(OSO)Ag(Se6)Ag(OSO)][Sb(OTeF5)6]2 1 and [(OSO)2Ag(Se6)Ag(OSO)2][Al(OC(CF3)3)4]2 2a. 1 could only be prepared by using bromine as co-oxidant, however, bulk 2b (2a with loss of SO2) was accessible from Ag[Al(OC(CF3)3)4] and grey Se in SO2 (chem. analysis). The reactions of Ag[MF6] (M= As, Sb) and elemental selenium led to crystals of 1/∞{[Ag(Se6)]∞[Ag2(SbF6)3]∞} 3 and {1/∞[Ag(Se6)Ag]∞}[AsF6]2 4. Pure bulk 4 was best prepared by the reaction of Se4[AsF6]2, silver metal and elemental selenium. Attempts to prepare bulk 1 and 3 were unsuccessful. 1–4 were characterized by single-crystal X-ray structure determinations, 2b and 4 additionally by chemical analysis and 4 also by X-ray powder diffraction, FT-Raman and FT-IR pectroscopy. Application of the PRESTO III sequence allowed for the first time 109Ag MAS NMR investigations of 4 as well as AgF, AgF2, AgMF6 and {1/∞[Ag(I2)]∞}[MF6] (M= As, Sb). Compounds 1 and 2a/b, with the very large counter ions, contain isolated [Ag(Se6)Ag]2+ heterocubane units consisting of a Se6 molecule bicapped by two silver cations (local D3d sym). 3 and 4, with the smaller anions, contain close packed stacked arrays of Se6 rings with Ag+ residing in octahedral holes. Each Ag+ ion coordinates to three selenium atoms of each adjacent Se6 ring. 4 contains [Ag(Se6)+]∞ stacks additionally linked by Ag(2)+ into a two dimensional network. 3 features a remarkable 3-dimensional [Ag2(SbF6)3]- anion held together by strong Sb–F … Ag contacts between the component Ag+ and [SbF6]- ions. The hexagonal channels formed by the [Ag2(SbF6)3]- anions are filled by stacks of [Ag(Se6)+]∞ cations. Overall 1–4 are new members of the rare class of metal complexes of neutral main group elemental clusters, in which the main group element is positively polarized due to coordination to a metal ion. Notably, 1 to 4 include the commonly metastable Se6 molecule as a ligand. The structure, bonding and thermodynamics of 1 to 4 were investigated with the help of quantum chemical calculations (PBE0/TZVPP and (RI-)MP2/TZVPP, in part including COSMO solvation) and Born–Fajans–Haber-cycle calculations. From an analysis of all the available data it appears that the formation of the usually metastable Se6 molecule from grey selenium is thermodynamically driven by the coordination to the Ag+ ions.
Item Type: | Journal article |
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Faculties: | Chemistry and Pharmacy |
Subjects: | 500 Science > 540 Chemistry |
URN: | urn:nbn:de:bvb:19-epub-15142-8 |
Alliance/National Licence: | This publication is with permission of the rights owner freely accessible due to an Alliance licence and a national licence (funded by the DFG, German Research Foundation) respectively. |
Language: | English |
Item ID: | 15142 |
Date Deposited: | 15. May 2013, 08:47 |
Last Modified: | 04. Nov 2020, 12:55 |