Synthesis and Reduction of Sterically Encumbered Mesoionic Carbene‐Stabilized Aryldihaloboranes

Arrowsmith, Merle; Böhnke, Julian; Braunschweig, Holger; Gao, Haopeng; Légaré, Marc‐André; Paprocki, Valerie; Seufert, Jens

doi:10.1002/chem.201700500

Cited by 28 publications

(20 citation statements)

References 94 publications

(72 reference statements)

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“…Dihaloborane triazolylidene adducts of type 142 were reported by Braunschweig and co-workers in analogy to the corresponding NHC-borane adducts. 123 The first MIC-supported diborane has also been synthesized by the same research group. In contrast, upon reduction of an MIC adduct, intramolecular C–H or C–C activation in the compound was observed instead ( 144 and 145 , Figure 10 ).…”

Section: Main Group Educts Of Micsmentioning

confidence: 99%

Chemistry of Compounds Based on 1,2,3-Triazolylidene-Type Mesoionic Carbenes

Maity

Sarkar

2021

JACS Au

106

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Mesoionic carbenes (MICs) of the 1,2,3-triazolylidene type have established themselves as a popular class of compounds over the past decade. Primary reasons for this popularity are their modular synthesis and their strong donor properties. While such MICs have mostly been used in combination with transition metals, the past few years have also seen their utility together with main group elements. In this paper, we present an overview of the recent developments on this class of compounds that include, among others, (i) cationic and anionic MIC ligands, (ii) the donor/acceptor properties of these ligands with a focus on the several methods that are known for estimating such donor/acceptor properties, (iii) a detailed overview of 3d metal complexes and main group compounds with these MIC ligands, (iv) results on the redox and photophysical properties of compounds based on MIC ligands, and (v) an overview on electrocatalysis, redox-switchable catalysis, and small-molecule activation to highlight the applications of compounds based on MIC ligands in contemporary chemistry. By discussing several aspects from the synthetic, spectroscopic, and application point of view of these classes of compounds, we highlight the state of the art of compounds containing MICs and present a perspective for future research in this field.

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Section: Main Group Educts Of Micsmentioning

confidence: 99%

Chemistry of Compounds Based on 1,2,3-Triazolylidene-Type Mesoionic Carbenes

Maity

Sarkar

2021

JACS Au

106

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“…N 2 O adduct 1 , 5 , and 7 were synthesized as described previously . 1‐(2,6‐Diisopropylphenyl)‐2‐methyl‐4‐phenyl‐1,2,3‐triazolium iodide was synthesized according to a published procedure . N 2 O (99.999 %) was purchased from Air‐liquide.…”

Section: Methodsmentioning

confidence: 99%

“…[12] 1-(2,6-Diisopropylphenyl)-2methyl-4-phenyl-1,2,3-triazolium iodide was synthesized according to ap ublished procedure. [25] N 2 O( 99.999 %) was purchased from Air-liquide. NMR spectra were measured with aB ruker Avance DPX-400 (1H:4 00 MHz).…”

Section: Methodsmentioning

confidence: 99%

Synthesis of Azo Dyes from Mesoionic Carbenes and Nitrous Oxide

Eymann

Scopelliti

Fadaei‐Tirani

et al. 2018

Chemistry A European J

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Covalent adducts of imidazole-based mesoionic carbenes and nitrous oxide (N O, "laughing gas") can be converted into azo dyes by reaction with arenes in the presence of AlCl or HCl. The azo coupling can be achieved with electron-rich aromatic compounds such as mesitylene, trimethoxybenzene, azulene, or dibenzo-18-crown-6. The latter coupling reaction allows for the easy preparation of a colorimetric sensor for potassium or sodium ions. As a putative intermediate of the reaction with acid, we were able to isolate and structurally characterize a rare diazohydroxide. Using imidazolium compounds with two N O groups, it was possible to prepare amine-substituted azo dyes or dyes with two azoarene groups attached to the heterocycle. A triazole-based mesoionic carbene was also found to form a stable covalent adduct with N O. The adduct could be used to prepare novel azo triazolium dyes in good yields.

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“…Many of these have demonstrated the formal insertion of a dicoordinate borylene fragment into intramolecular C-H bonds of the NHC ligand, similarly to free borylenes (Figure 26, B-D). [258][259][260] (44) and its trapping with naphthalene was invoked to explain the reactivity, the actual mechanism of the transformation is a subject of debate (Figure 27, A). 262 In a related reaction, our group also observed the formation of the remarkably robust borirane (Figure 27, B).…”

Section: Base-stabilized Borylenesmentioning

confidence: 99%

Metallomimetic Chemistry of Boron

2019

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The study of main-group molecules that behave and react similarly to transition metal (TM) complexes has attracted significant interest in the recent decades. Most notably, the attractive idea of eliminating the all-too-often rare and costly metals from catalysis has motivated efforts to develop main-group-element-mediated reactions. Main-group elements, however, lack the electronic flexibility of many TM complexes that arise from combinations of empty and filled d-orbitals and that seem ideally suited to bind and activate many substrates. In this Review, we look at boron, an element which, despite its non-metal nature, low atomic weight, and relative redox staticity has achieved great milestones in terms of TM-like reactivity. We show how in inter-element cooperative systems, diboron molecules and hypovalent complexes, the fifth element can acquire a truly metallomimetic character. As we discuss, this character is particularly strikingly demonstrated by the reactivity of boron-based molecules with H2, CO, alkynes, alkenes and even with N2.

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Synthesis and Reduction of Sterically Encumbered Mesoionic Carbene‐Stabilized Aryldihaloboranes

Cited by 28 publications

References 94 publications

Chemistry of Compounds Based on 1,2,3-Triazolylidene-Type Mesoionic Carbenes

Chemistry of Compounds Based on 1,2,3-Triazolylidene-Type Mesoionic Carbenes

Synthesis of Azo Dyes from Mesoionic Carbenes and Nitrous Oxide

Metallomimetic Chemistry of Boron

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