Rostock 2019 – wissenschaftliches Programm

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MO: Fachverband Molekülphysik

MO 19: Cluster III (joint session MO/A)

MO 19.6: Vortrag

Donnerstag, 14. März 2019, 12:00–12:15, S HS 001 Biologie

Superelectrophilic Behaviour of closo-Dodecaborate Monoanions — Knut R. Asmis¹, Martin Mayer¹, Jonas Warneke², and •Max Grellmann¹ — ¹Wilhelm-Ostwald-Institut für Physikalische und Theoretische Chemie, Universität Leipzig, Linnestr. 2, 04103 Leipzig (Germany) — ²Department of Chemistry, Purdue University, West Lafayette, IN 47907 (USA)

Bond formation with an electron-rich system, known as electrophilicity, is commonly observed in electron-deficient molecules. Binding noble gases at room temperature was a marking property predominantly of strong, dicationic systems, therefore termed as *superelectrophiles*. Gas-phase skimmer collision induced dissociation (sCID) lead to the formation of closo-dodecaborate monoanions [B12X11]-, showing a high reactivity towards electron-rich systems for instance dinitrogen, dioxygen and noble gases (Ngs). In particular, the clusters [B12X11]- (X = Cl, CN) have been observed to form spontaneously B-Ng bonds with a substantial degree of covalent interaction, thus showing a superelectrophilic behaviour despite being negatively charged. A significant blue shift of the CO stretching mode when bound with its carbon tail to a closo-dodecaborate monoanion, observed by using infrared photodissociation (IRPD) spectroscopy, verified the suspected electron-deficiency at the binding site of the cluster. Quantum chemical calculations revealed that the anions unite several molecular properties, which lead to a dipole discriminating chemistry, facilitating the addition of Ngs. On this account, small dipole moments of alkanes could be a promising property to introduce the anions into C-H-bond activation.