A Step Closer to Metal‐Free Dinitrogen Activation: A New Chapter in the Chemistry of Frustrated Lewis Pairs

Melen, Rebecca L.

doi:10.1002/anie.201711945

Cited by 81 publications

(67 citation statements)

References 12 publications

Supporting

Mentioning

Contrasting

Unclassified

Order By: Relevance

“…The NHC‐borane based FLP‐N 2 adducts 2.P2 and 4.P2 are significantly more stable (−55.0 and −61.7 kcal mol −1 ) than the corresponding NHC─N─N─borane adducts (−3.8 and 12.4 kcal mol −1 , respectively), and the latter can only lead to thermodynamically stable LA‐LB pair (Figure S7, Supporting Information). Similarly, previously isolable and thermodynamically favorable Lewis adduct Ph 2 C─N─N─B(C 6 F 5 ) 3 formed from diphenyldiazmehane and borane was proved to be highly unstable at ambient conditions to liberate N 2 molecule and a carbene‐borane adduct …”

Section: Resultsmentioning

confidence: 93%

“…Interestingly, Stephan, Grimme, and co‐workers described the formation of thermodynamically favorable Lewis adduct Ph 2 C─N─N─B(C 6 F 5 ) 3 from diphenyldiazomethane and borane species, where N 2 is considered trapped in between a carbene Lewis base (LB) and borane Lewis acid (LA) . However, a combined experimental and theoretical study revealed this adduct was only stable at low temperature and it was highly sensitive to liberate N 2 molecule along with a carbene‐borane adduct at ambient temperature conditions . Recently, Hogler Braunschweig et al .…”

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

Dinitrogen Activation by Tricoordinated Boron Species: A Systematic Design

Rouf

Dai

et al. 2020

Advcd Theory and Sims

View full text Add to dashboard Cite

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.

show abstract

Section: Resultsmentioning

confidence: 93%

Section: Introductionmentioning

confidence: 99%

Dinitrogen Activation by Tricoordinated Boron Species: A Systematic Design

Rouf

Dai

et al. 2020

Advcd Theory and Sims

View full text Add to dashboard Cite

show abstract

“…However, the metal‐free N 2 activation by FLP still remains elusive . Caulton and co‐workers designed a series of reactions which were thermodynamically favorable for N 2 functionalization by theoretical calculations in 2013.…”

Section: Figurementioning

confidence: 99%

“…[34] However,t he metal-free N 2 activation by FLP still remains elusive. [41,42] Caulton and co-workers [43] designedaseries of reactions which were thermodynamically favorable for N 2 functionalization by theoretical calculations in 2013. However,a ll these studies weref ocused on the thermodynamicso fr eactions whereas the kinetics remains unclear.I tis well known that at hermodynamically favorable reaction will not occur if its kinetics is not favorable.…”

mentioning

confidence: 99%

Rational Design of a Carbon‐Boron Frustrated Lewis Pair for Metal‐free Dinitrogen Activation

Zhu

2019

Chemistry An Asian Journal

View full text Add to dashboard Cite

Molecular nitrogen (N2) is abundant in the atmosphere and, found in many biomolecules, an essential element of life. The Haber–Bosch process, developed over 100 years ago, requires relatively harsh conditions to activate N2 on the iron surface and generate ammonia for use as fertilizer or to produce other chemicals, leading to consumption of more than 2 % of the world's annual energy supply. Thus, developing “green” approaches for N2 activation under mild conditions is particularly important and urgent. Here we demonstrate that a metal‐free N2 activation could be favorable both thermodynamically and kinetically (with an activation energy as low as 9.1 kcal mol−1) by using a carbon‐boron formal frustrated Lewis pair, which is supported by high‐level coupled cluster calculations. Mechanistic studies reveal that aromaticity plays a crucial role in stabilizing both the transition state and the product. Our findings highlight the importance of a combination of an N‐heterocyclic carbene with a methyleneborane unit in metal‐free N2 activation, providing conceptual guidance for experimental realization.

show abstract

“…Simonneau et al. classified the Group 6 metal analogues as transition‐metal frustrated Lewis pairs (TMFLPs)‐type activation of N 2 , and Tang et al . showed the first diazomethane‐B(C 6 F 5 ) 3 adduct, which features a bent B−N−N unit and is related to metal‐free FLP–N 2 capture (Figure d).…”

Section: Introductionmentioning

confidence: 91%

Two Push–Pull Channels Enhance the Dinitrogen Activation by Borylene Compounds

Zhang

Yuan

et al. 2020

Chemistry A European J

View full text Add to dashboard Cite

Recently, Braunschweig et al. found that borylene (CAAC)DurB, in which CAAC is a cyclic alkyl(amino) carbene and Dur refers to 2,3,5,6‐tetramethylphenyl, can bind and activate N2, and the resulting [(CAAC)DurB]2N2 is of a bent BNNB core. The N2 ligand in transition metal complexes is generally linear, so herein, the bonding nature of both terminal end‐on and end‐on bridging borylene‐N2 complexes is investigated with valence bond (VB) theory. In the terminal end‐on (CAAC)HBN2 the bonding follows the mechanism in transition metals with a σ donation and a π back‐donation, but in the end‐on bridging borylene‐N2 complex, the σ donation comes from the π orbitals of N2, and thus, there are two opposite and perpendicular push–pull channels. It is the push–pull interaction that governs the enhanced activation of N2 and the BNNB bent geometry. It is expected that the substituents bonded to B can modulate the bent angle and the strength of the push–pull interaction. Indeed, (CAAC)FB exhibits enhanced catalytic capacity for the activation of N2.

show abstract

A Step Closer to Metal‐Free Dinitrogen Activation: A New Chapter in the Chemistry of Frustrated Lewis Pairs

Cited by 81 publications

References 12 publications

Dinitrogen Activation by Tricoordinated Boron Species: A Systematic Design

Dinitrogen Activation by Tricoordinated Boron Species: A Systematic Design

Rational Design of a Carbon‐Boron Frustrated Lewis Pair for Metal‐free Dinitrogen Activation

Two Push–Pull Channels Enhance the Dinitrogen Activation by Borylene Compounds

Contact Info

Product

Resources

About