Main Group Redox Catalysis of Organopnictogens: Vertical Periodic Trends and Emerging Opportunities in Group 15

Abstract

A growing number of organo­pnicto­gen redox catalytic methods have emergedespecially within the past 10 yearsthat leverage the plentiful reversible two-electron redox chemistry within Group 15. The goal of this Perspective is to provide readers the context to understand the dramatic developments in organo­pnicto­gen catalysis over the past decade with an eye toward future development. An exposition of the fundamental differences in the atomic structure and bonding of the pnictogens, and thus the molecular electronic structure of organo­pnicto­gen compounds, is presented to establish the backdrop against which organo­pnicto­gen redox reactivityand ultimately catalysisis framed. A deep appreciation of these underlying periodic principles informs an understanding of the differing modes of organo­pnicto­gen redox catalysis and evokes the key challenges to the field moving forward. We close by addressing forward-looking directions likely to animate this area in the years to come. What new catalytic manifolds can be developed through creative catalyst and reaction design that take advantage of the intrinsic redox reactivity of the pnictogens to drive new discoveries in catalysis?

The inversion of tetrahedral p-block element compounds: general trends and the relation to the second-order Jahn–Teller effect

“…54 However, in recent years, several "anti-van't-Hoff-Le-Bel" species (i.e., stabilized inversion transition states), such as planar aluminates, silicon, or phosphonium ions, were isolated, offering unique reactivities. [55][56][57][58][59][60][61][62][63][64][65][66][67][68][69][70] Hence, knowledge on the tetrahedral inversion transforms from fundamental to applied interest.…”

Redox-Neutral Organometallic Elementary Steps at Bismuth: Catalytic Synthesis of Aryl Sulfonyl Fluorides

“…On one hand, the extensively studied and long-known Lewis acid catalysis, where the bismuth catalyst does not undergo redox processes or participate in catalytic organometallic elementary steps. 17 On the other hand, bismuth can undergo redox catalysis 18 through elementary organometallic steps, maneuvering between Bi(I)/(III), 19 Bi(II)/Bi(III), 20 or Bi(III)/(V) 21 ( Figure 1 B). Herein, we demonstrate that a third catalytic platform for bismuth can also be operative in the conversion of (hetero)aryl boronic acids to the corresponding sulfonyl fluorides.…”

High‐valent bismuth redox catalysis

“…Recently, elements of the group 15 have been at the center of attention as they have been shown to be applicable as catalysts in a myriad of organic transformations. 25) Indeed, strategies exploiting the use of their redox properties have recently been reported, 26) and even one-electron processes for Bi are beginning to have an impact in organic synthesis. 27) Multinuclear complexes, 28) ligand design, and indepth mechanistic studies will be essential to fully understand the underlying mechanisms of these transformations, leading to further discoveries through high-valent Bi redox catalysis.…”