Bismuthanylstibanes

Abstract

The first examples of neutral Bi–Sb σ-bonds are reported and their reactivity is debuted.

Aminobismuthination of CO2

“…6 In contrast to the facile insertion of CO2 into the very polarized M-N bonds of electropositive s/d/f-block metal amides, 3,[7][8][9][10] uncatalyzed insertion into less polar heavy p-block M-N bonds is kinetically challenging, and has therefore been studied to a limited extent. [11][12][13][14][15][16][17][18][19][20] As part of our ongoing exploration into the electronic structure and reactivity of pnictogen amides, [21][22][23][24][25][26] we considered the potential for CO2 activation with the heaviest family of such compounds -bismuth amides. Recent work showing that cationic and neutral bismuth amides can activate a host of challenging bonds established the prior plausibility of this endeavour.…”

Aminobismuthination of CO2

“…Nevertheless, the capture of CO2 is unambiguously confirmed by IR spectroscopy analysis of the reaction mixtures, which show diagnostic C=O stretching frequencies in the 1450-1650 cm -1 range (Supporting Information). To better control the selectivity of CO2 aminobismuthination, compound 4a 24,[41][42][43] was considered. Due to the greater basicity of alkylamides relative to arylamides and chelation enhanced stability of the Bi-N bonds involving the backbone, 4a was expected to exhibit more defined reactivity and yield either 4b or its dimer 4bdim.…”

Synthesis of a Molecule with Five Different Adjacent Pnictogens

“…Molecular compounds that contain different Group 15 elements are of general interest due to their specific bondings ituations and reactivity.V ery recently the first compound with a bismuth antimonys ingle bond could be obtained by S. Chitnis and co-workers. [1] The group of A. Schulz investigated in recent years the reactivity of hetrocyclic biradicaloids of the composition [E(m-NR)] 2 (E = P-Bi)a nd observed the activation of small molecules which exhibit single,d ouble or triple bonds. [2][3][4] Moreover,b inary molecular Group 15 compound are used as precursors in semiconductor production.…”

“…3 and 4 have already been prepared in the past, but for 4 no analytical data were provided. [32,33] NMR spectroscopy in C 6 D 6 of the compounds 2-4 was conducted at room temperature and for the 1 Hn ucleus (300 MHz) the resultsu nexpectedly differ (see Supporting Information ford etails). For 2 the spectrum exhibits two singlets:O ne located at 1.24 ppm with an integral of 9 and the other one at 1.46 ppm with an integral of 27 hydrogen atoms.…”