Catalytic Activation of N2O at a Low-Valent Bismuth Redox Platform

Yue Pang; Markus Leutzsch; Nils Nöthling; Josep Cornella

doi:10.1021/jacs.0c10092

Catalytic Activation of N₂O at a Low-Valent Bismuth Redox Platform

J Am Chem Soc. 2020 Nov 18;142(46):19473-19479. doi: 10.1021/jacs.0c10092. Epub 2020 Nov 4.

Authors

Yue Pang¹, Markus Leutzsch¹, Nils Nöthling¹, Josep Cornella¹

Affiliation

¹ Max-Planck-Institut für Kohlenforschung, Kaiser-Wilhelm-Platz 1, Mülheim an der Ruhr, 45470, Germany.

Abstract

Herein we present the catalytic activation of N₂O at a Bi^I⇄Bi^III redox platform. The activation of such a kinetically inert molecule was achieved by the use of bismuthinidene catalysts, aided by HBpin as reducing agent. The protocol features remarkably mild conditions (25 °C, 1 bar N₂O), together with high turnover numbers (TON, up to 6700) and turnover frequencies (TOF). Analysis of the elementary steps enabled structural characterization of catalytically relevant intermediates after O-insertion, namely a rare arylbismuth oxo dimer and a unique monomeric arylbismuth hydroxide. This protocol represents a distinctive example of a main-group redox cycling for the catalytic activation of N₂O.