Trinuclear Gold–Carborane Cluster as a Host Structure

Abstract

This work encompasses a comprehensive study of host–guest interactions between cyclic trimer metal–carborane [Au3(1,2‐C2B10H10)3]3– and several guest species such as cations (H+, Li+, Be2+, Hg2+), anions (F–, H–, Cl–, Br–, I–, HCC–), and neutral molecules (H2, CO2, I2, HCCH, N2). A computational study has been carried out to evaluate energetic profiles and determine the contribution of attractive or repulsive interactions between guest and host. The energy minima obtained call our attention to several cases. For instance, all above cations form stable minima as guest complexes with the three gold atoms of the host. Unexpectedly, pyramidal H– or F– species are obtained as energy minima, while other anions give completely repulsive interactions. Finally, the CO2 molecule is also trapped inside the trinuclear ring.

Hydrogen vs. Halogen Bonds in 1-Halo-Closo-Carboranes

“…The parent compound (closo-B 10 H 12 C 2 ) has three different isomers depending on the relative disposition of the compound (closo-B10H12C2) has three different isomers depending on the relative disposition of the carbon atoms: ortho (closo-1,2-dicarbadodecarborane), meta (closo-1,7-dicarbadodecarborane) and para (closo-1,12-dicarbadodecarborane) (Scheme 1). Theoretical studies of the interaction of carboranes with biomolecules by means of dihydrogen bonds [50], the hydrogen bond with π-systems [51,52], halogen bonds [53,54], interaction with gold derivatives [55,56] and as superacids [57] In this article, we studied the complexes between a Lewis base, hydrogen cyanide (NCH), used as a hydrogen bond (HB) and halogen bond (XB) acceptor probe and 1-halo-closo-carboranes (Scheme 2) acting as hydrogen-and halogen-bond donors. The parent compounds X = H have also been considered.…”

Do Gold(III) Complexes Form Hydrogen Bonds? An Exploration of AuIII Dicarboranyl Chemistry

“…[23] 1,2-Dicarboranyl ligands and the potentially chelating 2,2'-bis(dicarboranyl) dianion are more electron-withdrawingt han aryl ligands. [24] However,i nc ontrast to the large number of dicarboranyl derivatives of Au I , [25][26][27][28][29][30][31] to the best of our knowledge there are no reports of dicarboranyl complexes of gold(III). [32] We therefore explored synthetic routes to Au III complexes with [C 2 B 10 H 11 ] À and [2,2'-(C 2 B 10 H 10 ) 2 ] 2À ligands and report here the synthesis and structures of the first examples of well-characterised gold(III) dicarboranyl derivatives.…”

An experimental and computational NMR study of organometallic nine‐membered rings: Trinuclear silver(I) complexes of pyrazolate ligands

“…There are many representatives of compounds containing three ligands and three metals forming triangular shapes (Figure ). Imidazolates with coinage metals, phenylene (most examples correspond to o ‐tetrafluorophenylene) with mercury, 1,2‐dicarba‐ closo ‐dodecaboranes with Au(I), and pyrazolates with coinage metals (e.g., Table ). As the present study deals with the last class of complexes that are often designed by [M(μ‐Py)] 3 , and only for Ag(I), we have reported structural papers dealing with them in Table .…”