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

Abstract

Borane adducts of bis(di‐tert‐butylphosphanyl)amine (1a) and bis(di‐tert‐butylarsino)amine (1b) are reported. Based on quantum‐chemical investigations in combination with experimental results, it is demonstrated that the tautomerism known for tBu2P‐N(H)‐PtBu2 (1a), can be observed for the mono adduct tBu2P‐N(H)‐P(BH3)tBu2 (2a) as well, whereas for the corresponding arsenic compound 2b only one stable isomer is found. The bis‐borane adduct tBu2(BH3)As‐N(H)‐As(BH3)tBu2 (3b) is a rare example of a structurally characterized, tertiary arsine borane adduct, which can be directly compared with the corresponding phosphorus compound tBu2(BH3)P‐N(H)‐P(BH3)tBu2 (3a). Deprotonation of mixtures containing 2a by nBuLi leads to the lithium‐containing coordination polymer 4a, in which the actual chain consists only of non‐carbon atoms.

A surprise landing on the terra incognita of macrocyclic dibridgehead diorganoarsines: syntheses, structures, and reactivities

“…The addition of 1b and Me 2 S·BH 3 afforded the oily bis(borane) adduct 1b ·2BH 3 in 94% yield (Scheme 2). 1,21 As shown in Scheme 3, the reaction of 1c and PtCl 2 afforded the gyroscope like complex trans -Pt(Cl) 2 (As((CH 2 ) 14 ) 3 As) ( 4c , 86%), which is formally an adduct of in , in - 1c . Combining 1c and common NiCl 2 sources gave the nickel analog 5c (80–68%).…”