Cationic Chains of Phosphanyl‐ and Arsanylboranes

Abstract

Whilst catena-phosphorus cations have been intensively studied in the last years, mixed Group 13/15 element cationic chains have not yet been reported. Reaction of the pnictogenboranes H2EBH2⋅NMe3 (E=P, As) with monohalideboranes lead to the cationic chain compounds [Me3N⋅BH2EH2BH2⋅NMe3][X] (E=P, As; X=AlCl4 , I) and [Me3N⋅BH2PH2BH2PH2BH2⋅NMe3][X] (X=I, VCl4(thf)2), respectively. All of the compounds have been characterized by X-ray structure analysis, NMR spectroscopy, IR spectroscopy, and mass spectrometry. DFT calculations elucidate the reaction pathway, the high thermodynamic stability, the charge distribution within the chain and confirm the observed solid-state structures.

Monomeric phosphinoboranes

“…Off-metal oligomerisation to give the first examples of mixed Group 13/15 cationic chains (15 and 16) was achieved upon reaction of PH 2 BH 2 NMe 3 with monohaloboranes (Scheme 4) [41].…”

Ein Weg zu gemischten Pnictogenylboranen

“…[23,24] Die einzige bekannte längere neutrale Kette (V) [20] konnte nur durch NMR-Spektroskopie charakterisiert werden. Sowohl ihre hohe Flexibilitäta ls auch die fehlende Ionizitäte rschweren eine Charakterisierung im Festkçrper.I onizitätträgt entscheidend zur thermo-dynamischen Stabilitätdieser Art von Verbindungen bei.…”

Coordination of Boron‐centered Lewis Acids by organo‐substituted Phosphanylboranes

“…[10] Moreover, a series of oligomeric compounds containing unprecedented cationic and anionic chains of pnictogenylboranes could be obtained. [11] The introduction of alkyl-and aryl-substituents increases the solubility of the polymers. Such organo-substituted phosphanylboranes are excellent starting materials for poly(phosphinoboranes).…”