Organobismuth Redox Manifolds: Versatile Tools for Synthesis

Ruffell, Katie; Ball, Liam T.

doi:10.1016/j.trechm.2020.07.008

Cited by 19 publications

(17 citation statements)

References 10 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…As a result, several monometallic organobismuthanes have been explored as reagents for organic synthesis. 2 Compared to the vast literature on monometallic triarylbismuthanes, examples of bi- and dimetallic Bi complexes are much rarer and are mainly relegated to the low-valent counterparts Bi( i ) and Bi( ii ). Dimerization in these complexes is highly favored as a result of the unpaired electron in Bi( ii ) 3,4 or the stabilization of the highly reactive lone-pair in Bi( i ).…”

Section: Introductionmentioning

confidence: 99%

Dibismuthanes in catalysis: from synthesis and characterization to redox behavior towards oxidative cleavage of 1,2-diols

et al. 2021

View full text Add to dashboard Cite

show abstract

Section: Introductionmentioning

confidence: 99%

Dibismuthanes in catalysis: from synthesis and characterization to redox behavior towards oxidative cleavage of 1,2-diols

et al. 2021

View full text Add to dashboard Cite

show abstract

“…New developments that merge elementary organopnictogen redox reactions into catalytic cycles involving formal two-electron redox cycling have been gathering pace, especially within the past decade. These developments, proceeding in parallel with ongoing synthetic redox method developments elsewhere in the p -block in Groups 13, − 14, , 16, − and 17, − represent the vanguard of a new class of redox catalysts composed of main group elements that evoke an analogy with well-established activation modes of the late d -block elements. − …”

Section: Introductionmentioning

confidence: 99%

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

2021

View full text Add to dashboard Cite

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?

show abstract

“… 2 However, the intrinsic difficulties posed by the regeneration of low-valent species via RE limited the development of efficient catalytic redox processes based on main-group catalysts. 2b , 2c Located in the middle of the p-block, group 15 elements have recently been identified as privileged candidates to unfold redox catalysis, 3 as exemplified by the success of redox cycling using P and Bi redox couples in various catalytic reactions. 4 − 6 In this endeavor, our group reported catalytic C(sp 2 )–F and C(sp 2 )–OTf/ONf bond formation proceeding through canonical cross-coupling steps in a Bi(III)/Bi(V) manifold ( Figure 1 B).…”

mentioning

confidence: 99%

Catalytic Hydrodefluorination via Oxidative Addition, Ligand Metathesis, and Reductive Elimination at Bi(I)/Bi(III) Centers

et al. 2021

View full text Add to dashboard Cite

Herein, we report a hydrodefluorination reaction of polyfluoroarenes catalyzed by bismuthinidenes, Phebox-Bi(I) and OMe-Phebox-Bi(I). Mechanistic studies on the elementary steps support a Bi(I)/Bi(III) redox cycle that comprises C(sp 2 )–F oxidative addition, F/H ligand metathesis, and C(sp 2 )–H reductive elimination. Isolation and characterization of a cationic Phebox-Bi(III)(4-tetrafluoropyridyl) triflate manifests the feasible oxidative addition of Phebox-Bi(I) into the C(sp 2 )–F bond. Spectroscopic evidence was provided for the formation of a transient Phebox-Bi(III)(4-tetrafluoropyridyl) hydride during catalysis, which decomposes at low temperature to afford the corresponding C(sp 2 )–H bond while regenerating the propagating Phebox-Bi(I). This protocol represents a distinct catalytic example where a main-group center performs three elementary organometallic steps in a low-valent redox manifold.

show abstract

Organobismuth Redox Manifolds: Versatile Tools for Synthesis

Cited by 19 publications

References 10 publications

Dibismuthanes in catalysis: from synthesis and characterization to redox behavior towards oxidative cleavage of 1,2-diols

Dibismuthanes in catalysis: from synthesis and characterization to redox behavior towards oxidative cleavage of 1,2-diols

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

Catalytic Hydrodefluorination via Oxidative Addition, Ligand Metathesis, and Reductive Elimination at Bi(I)/Bi(III) Centers

Contact Info

Product

Resources

About