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Institute
- Institut für Physikalische und Theoretische Chemie (15) (remove)
A 1,8-naphthyridine diphosphine (NDP) reacts with boron-containing Lewis acids to generate complexes featuring a number of different naphthyridine bonding modes. When exposed to diborane B\(_{2}\)Br\(_{4}\), NDP underwent self-deprotonation to afford [NDP-B\(_{2}\)Br\(_{3}\)]Br, an unsymmetrical diborane comprised of four fused rings. The reaction of two equivalents of monoborane BBr\(_{3}\) and NDP in a non-polar solvent provided the simple phosphine-borane adduct [NDP(BBr\(_{3}\))\(_{2}\)], which then underwent intramolecular halide abstraction to furnish the salt [NDP-BBr\(_{2}\)][BBr\(_{4}\)], featuring a different coordination mode from that of [NDP-B\(_{2}\)Br\(_{3}\)]Br. Direct deprotonation of NDP by KHMDS or PhCH2K generates mono- and dipotassium reagents, respectively. The monopotassium reagent reacts with one or half an equivalent of B\(_{2}\)(NMe\(_{2}\))\(_{2}\)Cl\(_{2}\) to afford NDP-based diboranes with three or four amino substituents.
Bei der Einelektronenreduktion eines durch eine cyclisches (Alkyl)(amino)carben (CAAC) stabilisierten Arylborylen-Carbonylkomplexes erfolgt die Bildung eines dimeren Borylketyl-Radikalanions, bedingt durch eine intramolekulare Arylmigration zum CO Kohlenstoffatom. Computergestützte Analyse liefert Hinweise auf eine radikalanionische [(CAAC)B(CO)Ar]\(^{.-}\) Zwischenstufe. Weiterführende Reduktion des entstandenen Komplexes liefert ein hoch nukleophiles (Boranyliden)methanolat.
Twisted boron-based biradicals featuring unsaturated C\(_2\)R\(_2\) (R=Et, Me) bridges and stabilization by cyclic (alkyl)(amino)carbenes (CAACs) were recently prepared. These species show remarkable geometrical and electronic differences with respect to their unbridged counterparts. Herein, a thorough computational investigation on the origin of their distinct electrostructural properties is performed. It is shown that steric effects are mostly responsible for the preference for twisted over planar structures. The ground-state multiplicity of the twisted structure is modulated by the σ framework of the bridge, and different R groups lead to distinct multiplicities. In line with the experimental data, a planar structure driven by delocalization effects is observed as global minimum for R=H. The synthetic elusiveness of C\(_2\)R\(_2\)-bridged systems featuring N-heterocyclic carbenes (NHCs) was also investigated. These results could contribute to the engineering of novel main group biradicals.
The concepts of aromaticity and antiaromaticity have a long history, and countless demonstrations of these phenomena have been made with molecules based on elements from the p, d, and f blocks of the periodic table. In contrast, the limited oxidation‐state flexibility of the s‐block metals has long stood in the way of their participation in sophisticated π‐bonding arrangements, and truly antiaromatic systems containing s‐block metals are altogether absent or remain poorly defined. Using spectroscopic, structural, and computational techniques, we present herein the synthesis and authentication of a heterocyclic compound containing the alkaline earth metal beryllium that exhibits significant antiaromaticity, and detail its chemical reduction and Lewis‐base‐coordination chemistry.
The dimethylbismuth cation: entry into dative Bi-Bi bonding and unconventional methyl exchange
(2021)
The dimethyl bismuth cation, [BiMe\(_2\)(SbF\(_6\))], has been isolated and characterized. Reaction with BiMe\(_3\) allows access to the first compound featuring Bi→Bi donor–acceptor bonding. In solution, dynamic behavior with methyl exchange via an unusual S\(_E\)2 mechanism is observed, underlining the unique properties of bismuth species as soft Lewis acids with the ability to undergo reversible Bi−C bond cleavage.