Activation of atmospherically abundant dinitrogen (N2) by metal-free species under mild reaction conditions has been one the most challenging areas in chemistry for decades. Very recent but limited progress N2 activation boron species, including two-coordinated borylene and methyleneborane three-coordinated borole borane, made toward activation. Here, we systematically probe an experimentally viable frustrated Lewis pair (FLP) containing two moieties (methyleneborane carbene) via density...

Abstract Molecular nitrogen (N 2 ), an abundant component of the atmosphere, is appealing for industrial value‐added products. However, its intrinsic inertness limits activation to mainly metallic species. Environmental concerns and harsh reaction conditions have resulted in a demand alternate nonmetallic nontoxic routes activate functionalize N at ambient conditions. Comprehensive density functional theory (DFT) calculations are performed on by boron species, specifically experimentally...

Activation of the strongest triplet bond in molecular nitrogen (N2) under mild conditions is particularly challenging. Recently, its fixation and reduction were achieved by highly reactive dicoordinated borylene species at ambient conditions, ripping limits harsh reaction metallic species. Less with a facile preparation could be desirable for next-generation N2 activation. Now density functional theory calculations reveal that tricoordinated boranes potential candidate...

A graphene-based chemical sensor is fabricated which offers a notable response for nitrobenzene. The shows the highest sensitivity of 231.1 nitrobenzene and fastest 6.9 s benzyl chloride.

Carbon dioxide (CO2 , a common combustion pollutant) releasing continuously into the atmosphere is primarily responsible for rising atmospheric temperature. Therefore, CO2 sequestration has been an indispensable area of research past several decades. On other hand, concept aromaticity often employed in designing chemical reactions and metal-free frustrated Lewis pairs (FLPs) have proved ideal reagents to achieve reduction. However, considering FLP together less developed capture. Here we...

Dinitrogen (N2 ) activation is particularly challenging due to the significantly strong N≡N bond, let alone catenation of two N2 molecules. Recent experimental study shows that cyclic (alkyl)(amino)carbene (CAAC)-stabilized borylenes are able tackle and coupling below room temperature. Here we carry out density functional theory calculations explore corresponding reaction mechanisms. The results indicate barrier for dinitrogen by first borylene slightly higher than second borylene. In...

Quantum chemical calculations with the M06-2X, B3LYP, and B3LYP-D2 density functional theory methods were performed in order to examine formation of Brook-type silabenzenes 4a–n through [1,3]-trimethylsilyl (TMS) [1,3]-triisopropylsilyl (TIPS) shifts from a tetrahedral silicon atom an adjacent carbonyl oxygen cyclic conjugated acylsilane precursors. All silabenzenes, having 2-trialkylsiloxy substituent, are at lower relative energies than their The free energy activation M06-2X/6-311+G(d,p)...

On the basis of first-principles density functional theory calculations, we propose a new molecular photoswitch which exploits photochemical [1,3]-silyl(germyl) shift leading from silane to silene (a Si=C double bonded compound). The silanes investigated herein act as OFF state, with tetrahedral saturated silicon atoms disrupting conjugation through molecules. silenes, on other hand, have conjugated paths spanning over complete molecules and thus ON state. We calculate ON/OFF conductance...

Metallaaromatics have attracted considerable attention in recent years because they can display properties of both organic and organometallic species. However, it remains unclear whether Clar's rule could be applied to chemistry despite its proposal 1950s. Here, we investigate the relative stabilities 49 species by density functional theory (DFT) calculations. The results indicate that nonmetal-bridged isomers are more stable than metal-bridgehead ones, kinked linear isomers, extending aryne...

Abstract Unusual 1,2‐migration reactions of N‐heterocyclic carbene (NHC) on transition metals were investigated using density functional theory calculations. Our results reveal that the electronic properties, ring strain four‐membered ring, and aromaticity NHC play crucial roles in thermodynamics such a 1,2‐migration. Further studies show changing methylene metal center reactant with more electronegative group (NH or O) will lead to formation products nitrogen coordinating center, whereas...

Monosilicon analogs of phenolates and phenylthiolates are studied by quantum chemical calculations. Three different silaphenolates three silaphenylthiolates possible; the ortho-, meta-, para-isomers. For silaphenolates, meta-isomer is thermodynamically most stable, regardless if substituent R at Si H, t-Bu or SiMe3. However, with = H SiMe3 energy differences between isomers small, whereas ~5 kcal/mol more stable than ortho-isomer. ortho-isomer lowest energy, although ortho- meta-isomers...

The BN-doped organic analogues are interesting as aliphatic amineboranes for hydrogen storage, precursors aromatic borazines and adsorbent cage azaboranes. However, polyenes remained undeveloped. Herein, we perform theoretical calculations on two mono lower polyenes, 1,3-butadiene 1,3,5-hexatriene. A general rule is proposed, i.e., isomers with terminal nitrogen directly BN-connected, N-B(R), in particular, of significant thermodynamic stability compared their inverse (where boron at the...

Pentafulvenes are dipolar hydrocarbons since they shift their π-electrons to achieve Hückel aromaticity and thus the electron donating groups at exocyclic position can enhance aromaticity. Silapentafulvenes analogues of pentafulvene formed by replacement carbon atoms C[double bond, length as m-dash]C double bond with a silicon atom in pentafulvene. It remains unclear how 5-silapentafulvenes 6-silapentafulvenes be changed due polarization m-dash]Si bond. Here we perform density functional...

1H-azirine, a highly reactive, antiaromatic, and unstable tautomer of the aromatic, stable, (sometimes) isolable 2H-azirine, is stabilized, both thermodynamically kinetically, via an unprecedented route, where latter serves as precursor-exploiting electronic steric elements. Our density functional theory results invite experimentalists to realize 1H-azirine.

Abstract Chalcogenborines (or BX‐doped benzenes, where X=O/S) are interesting for intriguing photophysical and electronic properties. In spite of several advances, origin their relative thermodynamic stability remains elusive. Now, based on density functional theory (DFT) calculations, we reveal that the mono isomers (here called BX isomers) is in a good relation with geometry, natural bond orbital partial atomic charges (qs) bonding energy. Substitution by an electronegative F group...