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

Magre, Marc; Kuziola, Jennifer; Nöthling, Nils; Cornellà, Josep

doi:10.1039/d1ob00367d

Cited by 19 publications

(19 citation statements)

References 63 publications

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“…[16] Intramolecular close Bi•••Bi contacts with rigid bridging units were recently also investigated by J. Cornella and co-workers with distances of 3.807(1) Å and larger. [33] Other intermolecular short Bi•••Bi contacts in the literature have values of in 3.740(4) Å in (Me 3 Si) 2 BiBi(SiMe 3 ) 2 , 3.834(3)-3.873(3) Å in Bi {Co(CO) 4 } 3 , 3.8988(9) Å in Me 3 Bi or 3.9654(4) Å in Dipp 2 BiI (Dipp = 2,6-di-iso-propyl phenyl) and thus are slightly shorter or as long as the one in 10. [32,[34][35][36] Also similar to 9 is the strain of the As 2 N 2 ring which leads to a fold angle of 143.8(3)°, but in contrast to 9 there is no evidence of different conformations of the molecule in solution, since the signals in the NMR spectra are quite sharp.…”

Section: Further Substitution To 6-10mentioning

confidence: 99%

Structure and Reactivity of Alkaline Metal Bis(amido)diazadiarsetidinides

Ritter

Bergunde

Weigend

et al. 2021

Zeitschrift anorg allge chemie

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Dedication to Prof. Schnöckel on the Occasion of his 80th BirthdayA series of alkaline metal functionalised tert-butyl substituted bis(amido)diazadiarsetidinides [(μ-N(tBu)As) 2 (N(tBu)M) 2 ] (M = K (1), Rb (2), Cs (3), Na•thf (4), Na (5)) were prepared and their solid state structures investigated in detail. Further substitution reactions with tert-butyl substituted element chlorides of P, As, Sb and Bi were performed. The conversion of two equivalents tBu 2 AsCl (II) with 1-3 unexpectedly leads to the introduction of only one arsine moiety ([(μ-N(tBu)As) 2 (N(tBu)H)(N(tBu)AstBu 2 ] (6)) while the other nitrogen atom gets protonated by ether cleavage. The reaction of one equivalent tBuECl 2 (E = As (III), Sb (IV)) with 1, 2 or 3 yielded the intended cage compounds [(μ-N(tBu)As) 2 (NtBu) 2 EtBu] (E = As (7), Sb ( 8)) in high yields. Reaction of 1-3 with two equivalents of tBu 2 E'Cl (E' = Sb (V), Bi (VI)) yields the twofold substituted bis(amido)diazadiarsetidines [(μ-N(tBu) As) 2 (N(tBu)E'tBu 2 ) 2 ] (E' = Sb (9), Bi (10)), which show weak intramolecular E'-E' interactions.

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Section: Further Substitution To 6-10mentioning

confidence: 99%

Structure and Reactivity of Alkaline Metal Bis(amido)diazadiarsetidinides

Ritter

Bergunde

Weigend

et al. 2021

Zeitschrift anorg allge chemie

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“…Also polyaromatic sulfonyl fluorides ( 2n – o ) could be isolated in nearly quantitative yields. Contrary to previous Bi-catalyzed redox processes, this protocol exhibited high functional group compatibility. Indeed, boronic acids containing SiMe 3 ( 1p ), vinyl ( 1q ), alkynyl ( 1r ), formyl ( 1s ), and ester ( 1t ) were converted to their corresponding sulfonyl fluorides ( 2p – t ) in moderate to good yields.…”

mentioning

confidence: 91%

“…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.…”

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confidence: 99%

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

Magre

Cornellà

2021

J. Am. Chem. Soc.

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A Bi-catalyzed synthesis of sulfonyl fluorides from the corresponding (hetero)aryl boronic acids is presented. We demonstrate that the organobismuth(III) catalysts bearing a bis-aryl sulfone ligand backbone revolve through different canonical organometallic steps within the catalytic cycle without modifying the oxidation state. All steps have been validated, including the catalytic insertion of SO 2 into Bi–C bonds, leading to a structurally unique O-bound bismuth sulfinate complex. The catalytic protocol affords excellent yields for a wide range of aryl and heteroaryl boronic acids, displaying a wide functional group tolerance.

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“… Finally, dinuclear or multinuclear complexes with mixed oxidation states would also allow one to discover new redox chemistry. 76 …”

Section: Conclusion and Future Outlookmentioning

confidence: 99%

Bismuth Redox Catalysis: An Emerging Main-Group Platform for Organic Synthesis

2022

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Bismuth has recently been shown to be able to maneuver between different oxidation states, enabling access to unique redox cycles that can be harnessed in the context of organic synthesis. Indeed, various catalytic Bi redox platforms have been discovered and revealed emerging opportunities in the field of main group redox catalysis. The goal of this perspective is to provide an overview of the synthetic methodologies that have been developed to date, which capitalize on the Bi redox cycling. Recent catalytic methods via low-valent Bi(II)/Bi(III), Bi(I)/Bi(III), and high-valent Bi(III)/Bi(V) redox couples are covered as well as their underlying mechanisms and key intermediates. In addition, we illustrate different design strategies stabilizing low-valent and high-valent bismuth species, and highlight the characteristic reactivity of bismuth complexes, compared to the lighter p -block and d -block elements. Although it is not redox catalysis in nature, we also discuss a recent example of non-Lewis acid, redox-neutral Bi(III) catalysis proceeding through catalytic organometallic steps. We close by discussing opportunities and future directions in this emerging field of catalysis. We hope that this Perspective will provide synthetic chemists with guiding principles for the future development of catalytic transformations employing bismuth.

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

Abstract: A family of novel dimetallic Bi(iii) and Bi(v) complexes is reported. Structural analysis of the complexes in the solid state permitted the study of the Bi–Bi distance and its impact in the catalytic redox properties.

Cited by 19 publications

References 63 publications

Structure and Reactivity of Alkaline Metal Bis(amido)diazadiarsetidinides

Structure and Reactivity of Alkaline Metal Bis(amido)diazadiarsetidinides

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

Bismuth Redox Catalysis: An Emerging Main-Group Platform for Organic Synthesis

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