The Oxidation of Triethylbismuth

Abstract

It is generally known1 that trialkylbismuth compounds are oxidized by air at ordinary temperatures so rapidly that they ignite spontaneously, in some cases with explosive violence.5 Under these conditions the bismuth compound is probably oxidized completely to bismuth trioxide. Reports of studies on the intermediate steps or of the mechanism of such oxidations have not appeared in the literature. It was the purpose of the present work to study the oxidation of triethylbismuth under controlled conditions with the view of isolating and identifying both the intermediate and final products of oxidation, and, if possible, to determine the mechanism of such an oxidation.Such a study has been carried out by treating triethylbismuth stepwise with oxygen under carefully controlled temperature conditions, collecting and isolating the various gaseous, liquid, and solid products formed in each step, and identifying the various products by analyses or other suitable means.

Efficient Fixation of Carbon Dioxide by Hypervalent Organobismuth Oxide, Hydroxide, and Alkoxide

“…8 The 5,6,7,12‐tetrahydrodibenz[c,f][1,5]azabismocine framework is highly stable as a diorganobismuth fragment and, therefore, is suitable for the study of diorganobismuth compounds bearing various heteroatom groups on the bismuth atom. Since structural and reactivity studies of diorganobismuth(III) hydroxides,5, 9 oxides,5, 9, 10 and alkoxides9, 11 are limited, we examined the synthesis of such compounds with the 5,6,7,12‐tetrahydrodibenz[c,f][1,5]azabismocine framework. In analogy to the synthesis of {(2,4,6‐Me 3 C 6 H 2 ) 2 Bi} 2 O 2 ,10d bismuth chloride 3 was treated with aqueous sodium hydroxide solution, and subsequent recrystallization of the crude product from toluene under nitrogen exclusively afforded bismuth oxide 6 .…”

Direct N-Cyclopropylation of Cyclic Amides and Azoles Employing a Cyclopropylbismuth Reagent

“…14 Contrary to other alkylbismuth reagents, tricyclopropylbismuth was found to be nonpyrophoric. 15 Therefore, simple workup and trituration in hexanes provided 2a as a white solid. 16 Mass spectroscopy experiments confirmed the presence of tricyclopropylbismuth.…”

Efficient Fixation of Carbon Dioxide by Hypervalent Organobismuth Oxide, Hydroxide, and Alkoxide

“…[7,8] The 5,6,7,12-tetrahydrodibenz[c,f]-[1,5]azabismocine framework is highly stable as a diorganobismuth fragment and, therefore, is suitable for the study of diorganobismuth compounds bearing various heteroatom groups on the bismuth atom. Since structural and reactivity studies of diorganobismuth(III) hydroxides, [5,9] oxides, [5,9,10] and alkoxides [9,11] are limited, we examined the synthesis of such compounds with the 5,6,7,12-tetrahydrodibenz[c,f]-[1,5]azabismocine framework. In analogy to the synthesis of {(2,4,6-Me 3 C 6 H 2 ) 2 Bi} 2 O 2, [10d] bismuth chloride 3 was treated with aqueous sodium hydroxide solution, and subsequent recrystallization of the crude product from toluene under nitrogen exclusively afforded bismuth oxide 6.…”