The Lewis‐Base‐Stabilized Diphenyl‐Substituted Arsanylborane: A Versatile Building Block for Arsanylborane Oligomers

Abstract

The synthesis and properties of the diphenyl-substituted arsanylborane Ph AsBH SMe (1) and Ph AsBH NMe (2) stabilized by a Lewis base (LB) were reported. These compounds were obtained by reaction of KAsPh with IBH -LB (LB=SMe , NMe ). Compounds 1 and 2 were used as starting materials for oligomeric/ polymeric arsinoboranes. The neutral species, H B-Ph AsBH NMe (3) and Br B-Ph AsBH NMe (4), were synthesized by reaction with H B and Br B, respectively. Upon reaction with IBH -LB (LB=SMe , NMe ), the cationic oligomeric group-13/15-based compounds [(Me NBH AsPh BH NMe )]I (5) and [H B(Ph AsBH NMe ) ]I (6) were obtained. All compounds were completely characterized. In addition, the oxidation of Ph AsBH NMe with chalcogens was studied. The sulfur Ph As(S)BH NMe (7 b) and selenium Ph As(Se)BH NMe (7 c) oxidation products were both isolated and fully characterized, whereas the bis(trimethylsilyl)peroxide oxidated arsinoborane Ph As(O)BH NMe (7 a) was not stable enough and could only be characterized in solution. DFT computations supported the decomposition pathway of this compound.

Functional Polymeric Materials Based on Main‐Group Elements

“…[76] Thed iisopropylamino component of the DIAB precursor can be exchanged at À40 8 8Cw ith other primary alkylamines,t hus further expanding the scope of Nalkyl substituted poly(aminoborane)s.R ecent studies by Scheer et al indicate that this approach may also offer access to some of the heavier analogues,s uch as polymers containing alternating As and Ba toms in the main chain. [77] High molecular weight poly(aminoborane)s with aromatic substituents on B(39, M n = 81.6 and 86.8 kDa, Figure 8) have been realized by Manners et al using arylborane adducts NH 3 ·BH 2 R( R = Ph, p-CF 3 C 6 H 4 )a sp recursors. [72] Related hybrid materials with aromatic and aliphatic linkers can be obtained by condensation of bis(boronic acid) building blocks and bis(ammonium) salts with LiAlH 4 (40, Figure 8).…”

“…The diisopropylamino component of the DIAB precursor can be exchanged at −40 °C with other primary alkylamines, thus further expanding the scope of N‐alkyl substituted poly(aminoborane)s. Recent studies by Scheer et al. indicate that this approach may also offer access to some of the heavier analogues, such as polymers containing alternating As and B atoms in the main chain …”

Funktionelle polymere Materialien auf der Basis von Hauptgruppen‐Elementen

“…BH 3 (Abbildung 8, oben links). [77] Poly ( BH 2 R( R= Ph, p-CF 3 C 6 H 4 )a ls Vorstufen hergestellt. {75] Vork urzem entdeckten Alcaraz et al einen metallfreien Wegm it Diisopropylaminoboran (iPr 2 NBH 2 ,D IAB) als Boranquelle,d er außergewçhnlich hochmolekulare Poly(aminoborane) (M n = 170-5450 kDa) liefert (Abbildung 8, oben rechts).…”

“…B. Polymere,die abwechselnd As-und B-Atome in der Hauptkette enthalten. [77] Poly ( [79] Diese Polymere kçnnen als Analoga von Polyacetylenen angesehen werden, jedoch sind die B-N-Bindungen polarisiert, und der Doppelbindungscharakter ist gering; daher fehlt ihnen eine signifikante Verlängerung der Konjugation.…”

Small Chains of Main Group Elements by BH3 Adduct Formation of tBu2E‐N(H)‐EtBu2 (E = P, As)

“…for certain substituents an equilibrium with a tautomer (1a 1 ) is observed. [9] For the heavier homologue arsenic, a number of arsines including tBu 2 As-N(H)-AstBu 2 are well-known, [10] but their corresponding BH 3 adducts [11][12][13] as well as adducts with haloboranes are in contrast exceedingly rare. [14,15] Oligomers and polymers, in which the main chain is based on elements other than carbon, gained increasing attention in recent years.…”