Predicting Dinitrogen Activation by Boron Radical Cations

Inorganic Chemistry, Journal Year: 2025, Volume and Issue: unknown

Published: Feb. 3, 2025

Activation of dinitrogen (N2) under mild conditions has been a particularly challenging project for decades, owing to the highly strong N≡N triple bond. In recent years, main group species have emerged as prominent strategy in field activation, but reported examples remain rare compared with transition metal complexes. Herein, we performed comprehensive density functional theory (DFT) calculation N2 activation by boron radical cations. The calculations demonstrated that cations was favorable both kinetically and thermodynamically, high exothermicity (ΔG value -36.8 kcal/mol) low reaction barrier (7.3 kcal/mol), indicating feasibility conditions. Moreover, principal interacting spin orbitals (PISOs) intrinsic bond (IBOs) analyses revealed cation activated through two perpendicular interactions, including σ-type donation π-type backdonation. Additionally, further analysis implied backdonation is essential activation. Our findings offer an alternative approach metal-free highlighting significance chemistry

Language: Английский

Exploring N2 activation using novel Lewis acid/base pairs: computational insight into frustrated Lewis pair reactivity†

Dalton Transactions, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 1, 2025

The activation of dinitrogen (N2) is a crucial step in synthesizing nitrogen-based compounds and remains significant challenge due to its strong triple bond. Currently, industrial N2 conversion relies on the Haber-Bosch process, highly energy-intensive method that utilizes transition metal-based catalysts. Frustrated Lewis pairs (FLPs) have emerged as promising alternative for without need metals. In this work, we employ density functional theory (DFT) investigate by metal-free acids (LAs) bases (LBs). Our study demonstrates LAs play role capturing determining thermodynamics activation, while LBs complementary reducing bond order molecule, thereby promoting activation. efficiency capture directly linked electroaccepting characteristics LAs. A principal component analysis (PCA) reveals key factors influencing power are degree pyramidalization orbital occupation at acidic site, well local electrophilicity index. LA-N2 interaction found be electrostatic with partially covalent character. Among 21 analyzed, triptycene-based systems exhibit highest stability forming complexes, highlighting their potential effective N2-capturing agents. However, largely intact, necessitating involvement LA-N2-LB complexes full "push-pull" mechanism. Six analyzed most Bonding indicates LB-N2 can regarded bond, which may explain main LB reduction order. Furthermore, significantly enhanced increasing nucleophilicity LB. all LA-LB pair combinations, only three defining frustrated (FLPs), moderate energies substantial distances. findings suggest FLPs composed tris-tert-butylphosphine represent candidates

Language: Английский

Predicting σ⁰π² Carbene-Mediated Hydroboration and Bis-carbene Functionalization of Dinitrogen

Inorganic Chemistry, Journal Year: 2025, Volume and Issue: unknown

Published: May 9, 2025

Although the carbene-catalyzed N2 fixation process had been investigated by scientists for decades prior to borylene species, interest in carbene-mediated activation has drawn less attention than that of species past few years, especially unique σ0π2 carbenes. Herein, we demonstrate important role carbenes 1,1-hydroboration and bis-carbene functionalization using density functional theory calculations. Both being kinetically thermodynamically favorable, reaction barriers are as low 13.7 16.6 kcal/mol, respectively. Additionally, such a carbene can also achieve series X-H insertion reactions (X = H, CH3, Bpin, or SiH2Ph), with energies ranging from 8.2 15.3 kcal/mol. Our findings highlight strong potential electronic configuration its versatile transformations, providing valuable insights into main-group-element-mediated chemistry.

Language: Английский