Metastable Se6 as a ligand for Ag+: from isolated molecular to polymeric 1D and 2D structures

Attempts to prepare the hitherto unknown Se(6)(2+) cation by the reaction of elemental selenium and AgA] (A](-) = Sb(OTeF(5))(6)](-), Al(OC(CF(3))(3))(4)](-)) in SO(2) led to the formation of (OSO)Ag(Se(6))Ag(OSO)]Sb(OTeF(5))(6)](2)1 and (OSO)(2)Ag(Se(6))Ag(OSO)(2)]Al(OC(CF(3))(3))(4)](2)2a. 1 could only be prepared by using bromine as co-oxidant, however, bulk 2b (2a with loss of SO(2)) was accessible from AgAl(OC(CF(3))(3))(4)] and grey Se in SO(2) (chem. analysis). The reactions of AgMF(6)] (M = As, Sb) and elemental selenium led to crystals of 1/∞{Ag(Se(6))](∞)Ag(2)(SbF(6))(3)](∞)} 3 and {1/∞Ag(Se(6))Ag](∞)}AsF(6)](2)4. Pure bulk 4 was best prepared by the reaction of Se(4)AsF(6)](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 spectroscopy. Application of the PRESTO III sequence allowed for the first time (109)Ag MAS NMR investigations of 4 as well as AgF, AgF(2), AgMF(6) and {1/∞Ag(I(2))](∞)}MF(6)] (M = As, Sb). Compounds 1 and 2a/b, with the very large counter ions, contain isolated Ag(Se(6))Ag](2+) heterocubane units consisting of a Se(6) molecule bicapped by two silver cations (local D(3d) sym). 3 and 4, with the smaller anions, contain close packed stacked arrays of Se(6) rings with Ag(+) residing in octahedral holes. Each Ag(+) ion coordinates to three selenium atoms of each adjacent Se(6) ring. 4 contains Ag(Se(6))(+)](∞) stacks additionally linked by Ag(2)(+) into a two dimensional network. 3 features a remarkable 3-dimensional Ag(2)(SbF(6))(3)](-) anion held together by strong Sb-FAg contacts between the component Ag(+) and SbF(6)](-) ions. The hexagonal channels formed by the Ag(2)(SbF(6))(3)](-) anions are filled by stacks of Ag(Se(6))(+)](∞) 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 Se(6) 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 Se(6) molecule from grey selenium is thermodynamically driven by the coordination to the Ag(+) ions.