Thermal C–H borylation using a CO-free iron boryl complex

Mazzacano, Thomas J.; Mankad, Neal P.

doi:10.1039/c4cc09180a

Cited by 34 publications

(19 citation statements)

References 30 publications

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“…18 In fact, complete removal of the SBCO ligands from the catalyst design shuts off C-H borylation catalysis. 19 While the structural identification and parameterization of SBCO ligands is decades old, a rigorous analysis of their structural data in the broad context of bimetallic carbonyl complexes has not been undertaken since the advent of easily searchable structural databases and the large datasets they provide. 20 In this article, we briefly summarize the history of SBCO structures, provide a re-evaluation of this literature based on a data-intensive search of the Cambridge Structural Database (CSD), and present computational data clarifying the strength (or lack thereof ) of the SBCO interaction.…”

Section: Neal P Mankadmentioning

confidence: 99%

A data-intensive re-evaluation of semibridging carbonyl ligands

Parmelee

Mankad

2015

Dalton Trans.

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Structural data pertaining to bimetallic complexes with semibridging carbonyl (SBCO) ligands are analyzed using a comprehensive search of the Cambridge Structural Database (CSD). A brief review of the history of SBCO structures is presented, and this history is evaluated in light of the vastly larger dataset available today from the CSD. Additionally, computational analysis is used to reinforce conclusions from the structural data analysis, as well as to estimate the strength of a typical SBCO interaction. In view of the increasing number of research groups pursuing bimetallic strategies in inorganic/organometallic chemistry, this study adds to the understanding regarding an interaction type that, while weak, is known to play important structural and kinetic roles in certain systems.

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Section: Neal P Mankadmentioning

confidence: 99%

A data-intensive re-evaluation of semibridging carbonyl ligands

Parmelee

Mankad

2015

Dalton Trans.

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“…We were successful in synthesizing several CpFe(PR 3 ) 2 (Bpin) derivatives and found that Cp-Fe(PEt 3 ) 2 (Bpin) was able to borylate arene solvents in the absence of light at temperatures as low at 70 °C. 54 Unfortunately, catalysis was not possible in this case because the byproduct of C-H borylation, CpFe(PEt 3 ) 2 H, was not observed to react with any (NHC)CuH partner (Scheme 2), thus eliminating the possibility of a thermal analogue of the cycle shown in Scheme 1c. The facile H 2 elimination reaction in our original system was driven by the hydridic…”

Section: Pursuit Of Thermal Borylation Conditionsmentioning

confidence: 99%

Pursuit of C–H Borylation Reactions with Non-Precious Heterobimetallic Catalysts: Hypothesis-Driven Variations on a Design Theme

Leon¹,

Yu²,

Mazzacano³

et al. 2019

Synlett

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This article presents a retrospective account of our group’s heterobinuclear (NHC)Cu-[MCO] catalyst design concept (NHC = N-heterocyclic carbene, [MCO] = metal carbonyl anion), the discovery of its application towards UV-light-induced dehydrogenative borylation of unactivated arenes, and the subsequent pursuit of thermal reaction conditions through structural modifications of the catalysts. The account highlights advantages of using a hypothesis-driven catalyst design approach that, while often fruitless with regard to the target transformation in this case, nonetheless vastly expanded the set of heterobinuclear catalysts available for other applications. In other words, curiosity-driven research conducted in a rational manner often provides valuable products with unanticipated applications, even if the primary objective is viewed to have failed.1 Introduction to Heterobinuclear Catalysts for C–H Borylation2 Pursuit of Thermal Borylation Conditions3 Catalysts beyond Copper Carbenes4 Conclusions

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“…Direct C(sp 2 )-H borylation offers a simple and efficient route to aryl-boronic esters, which are key platforms for organic synthesis [13][14][15]. Iridium-based complexes have become a "go-to" for C(sp 2 )-H borylation reactions [16][17][18][19][20][21][22][23][24], while the discovery and development of Earth-abundant alternatives remains comparatively rare [25][26][27][28][29][30][31][32][33][34][35][36][37].…”

Section: Introductionmentioning

confidence: 99%

Iron-Catalysed C(sp2)-H Borylation Enabled by Carboxylate Activation

Britton

Docherty

Dominey³

et al. 2020

Molecules

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Arene C(sp2)-H bond borylation reactions provide rapid and efficient routes to synthetically versatile boronic esters. While iridium catalysts are well established for this reaction, the discovery and development of methods using Earth-abundant alternatives is limited to just a few examples. Applying an in situ catalyst activation method using air-stable and easily handed reagents, the iron-catalysed C(sp2)-H borylation reactions of furans and thiophenes under blue light irradiation have been developed. Key reaction intermediates have been prepared and characterised, and suggest two mechanistic pathways are in action involving both C-H metallation and the formation of an iron boryl species.

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Thermal C–H borylation using a CO-free iron boryl complex

Cited by 34 publications

References 30 publications

A data-intensive re-evaluation of semibridging carbonyl ligands

A data-intensive re-evaluation of semibridging carbonyl ligands

Pursuit of C–H Borylation Reactions with Non-Precious Heterobimetallic Catalysts: Hypothesis-Driven Variations on a Design Theme

Iron-Catalysed C(sp2)-H Borylation Enabled by Carboxylate Activation

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