NHCs in Main Group Chemistry

Nesterov, V. I.; Reiter, Dominik; Bag, Prasenjit; Frisch, Philipp; Holzner, Richard; Porzelt, Amelie; Inoue, Shigeyoshi

doi:10.1021/acs.chemrev.8b00079

Cited by 631 publications

(502 citation statements)

References 1,079 publications

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“…Owing to the development of novel synthetic strategies and versatile applicability, NHCs have gained considerable attention . Based on several studies highlighting reactivity of NHCs, cyclic alkyl amino carbenes (CAACs) proved to be more reactive than that of cyclic diamino carbenes (CDACs), due to the presence of one nitrogen atom and σ‐donating tetravalent carbon that decreases their HOMO‐LUMO gaps with the slightly higher HOMO . Therefore, CAACs acquire stronger σ‐donating and improved π‐accepting properties (Figure 1c), as indicated by the activation of H 2 , CO, and NH 3 .…”

Section: Resultsmentioning

confidence: 99%

Dinitrogen Activation by Tricoordinated Boron Species: A Systematic Design

Rouf

Dai

et al. 2020

Advcd Theory and Sims

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Molecular nitrogen (N2), an abundant component of the atmosphere, is appealing for industrial value‐added products. However, its intrinsic inertness limits its activation to mainly metallic species. Environmental concerns and harsh reaction conditions have resulted in a demand for alternate nonmetallic and nontoxic routes to activate and functionalize N2 at ambient conditions. Comprehensive density functional theory (DFT) calculations are performed on N2 activation by boron species, specifically for the experimentally more accessible tricoordinated boron compounds. Subsequently designed frustrated Lewis pairs (FLPs) combining screened N‐heterocyclic carbene with boron moieties can make N2 activation both kinetically and thermodynamically favorable, displaying high potential for metal‐free N2 activation. The significant thermodynamic stability of the products stabilized by aromaticity and low activation barriers could be a breakthrough for the development of FLP chemistry on metal‐free N2 activation.

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Section: Resultsmentioning

confidence: 99%

Dinitrogen Activation by Tricoordinated Boron Species: A Systematic Design

Rouf

Dai

et al. 2020

Advcd Theory and Sims

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“…Other carbenes that have been used in the synthesis of carbones are CAACs. These ligands are stronger π acceptors than NHCs . Moreover, the syntheses of [3]cumulenes with CAACs as terminal groups have been successful, contrary to NHCs .…”

Section: Resultsmentioning

confidence: 99%

How to Bend a Cumulene

Barquera‐Lozada

2020

Chemistry A European J

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Allenes (carbodicarbenes) and [3]cumulenes are linear carbon chains that can be bent when the terminal group has a strong carbene nature. This bending can be quite pronounced in allenes but not in [3]cumulenes. In this study, how N‐heterocyclic or cyclic (alkyl)(amino) carbene (NHC and CAAC, respectively) terminal groups can modify the linear structure of [n]cumulenes has been analyzed. A low π acidity of the terminal carbene affects the linearity of [2n]cumulenes. Indeed, it has been found that the NHC [4]cumulene is extremely bent, contrary to classical [4]cumulenes. The predicted NHC [4]cumulene or tricarbodicarbene has two lone pairs and the π electrons are delocalized over the whole molecule. More significantly, DFT calculations have shown that this bent [4]cumulene is very stable, considerably more so than the corresponding [3]cumulene, which has been elusive to synthesize. Remarkably, calculations have shown that all the NHC [2n]cumulenes are more than 25 kcal mol−1 more stable than the [2n−1]cumulenes.

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“…Several types of ligands have been employed for this, but by far the most common are N‐heterocyclic carbenes (NHCs). NHCs have found widespread use in low‐valent main group chemistry, and here is no exception. As well as being strong σ‐donors, positive charge can be effectively delocalised within them to provide further stabilisation of cationic species.…”

Section: Introductionmentioning

confidence: 99%

NHC‐Stabilised Silyliumylidene Ions

Powley

Inoue

2019

The Chemical Record

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Donor‐stabilised silyliumylidene ions, from the parent [R−Si:]+, are a class of low‐valent silicon species which have received increasing research interest in the last several years. This interest began in the fundamental synthesis and characterisation of these compounds, but has since started to include more investigation into their further reactivity after several stable NHC‐stabilised silyliumylidene ions were reported. This personal account briefly discusses the history of the still‐young field of silyliumylidene ions followed by a more detailed discussion of published work from our group on the further development of silyliumylidene chemistry over the last four years.

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NHCs in Main Group Chemistry

Cited by 631 publications

References 1,079 publications

Dinitrogen Activation by Tricoordinated Boron Species: A Systematic Design

Dinitrogen Activation by Tricoordinated Boron Species: A Systematic Design

How to Bend a Cumulene

NHC‐Stabilised Silyliumylidene Ions

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