Highlights with ‘Reactivity’

A general Pd-catalyzed pathway to β-lactams

In a recent Science paper the Gaunt group reports facile access to β-lactams via palladium-catalyzed coupling of aliphatic amines and carbon monoxide. The scope of the reaction is remarkably broad; over 40 substrates are illustrated, bearing a...

Spin Orbit Coupling effect on spin-forbidden reaction mechanisms

A spin forbidden reaction occurs with a change of the total electronic spin from reactants to products. The mechanistic study is therefore not trivial, since the reaction does not occur on a single adiabatic potential...

H2 production by PAH gasification

The gasification of polycyclic aromatic hydrocarbons (PAHs) in supercritical water has been studied with a DFT and ReaxFF. Supercritical water decreases the barrier for the rate-determining ring opening of PAHs by over 550 kJ/mol, thereby accelerating...

Counterion effect in NHC-gold(I)-catalyzed alkoxylation

Homogeneous gold catalysis has reached an extraordinary level of popularity within organic synthesis as a fundamental tool in the nucleophilic reactions of isolated π-systems, C-H  activation,  cross-couplings, photocatalysis and enantioselective transformations. Together with the ligand...

Highly accelerated strain-promoted azide-alkyne cycloadditions

In a joint experimental-theoretical effort reported in Nature Communications, highly accelerated azide-cycoalkyne have been achieved and analyzed with DFT. The ‘click’ type reaction has also been demonstrated in a one-pot three-component protein labeling reaction and...

Intramolecular 6-electron photo-redox reactions

Oxidative addition and reductive elimination reactions of small molecules possessing high-order bonds (e.g. N2, O2, NO+) is of fundamental interest in transition metal chemistry. As a means to study the mechanism and intermediates of such...

Growth Mechanism of Small Endohedral Metallofullerenes

In two recent combined experimental and computational studies, the optimal cage for each endohedral metallofullerene within the families Ti@C2n and Ca@C2n has been identified and key aspects of the intriguing growth mechanisms of fullerenes were unravelled....

Zeolite-catalyzed hydrolysis: DFT/DFTB calculations

The catalytic hydrolysis of propylene oxide in ZSM-5 was investigated using multi-layered ADF/DFTB calculations with QUILD. Using dispersion-corrected DFT (BP86-D3) at the high level and third-order DFTB (DFTB3) at the low level,  both monopropylene glycol and dipropylene...

Intersystem crossing through spin-orbit coupling in Os(II) complexes

The Os(fipz)(tfa)(CO)3 (tfa = trifluoroacetate, fipz=3-trifluoromethyl-5-(1-isoquinolinyl)-1,2-pyrazole) complex shows excitation-dependent emission quantum yield. The higher-energy excitation (< 340 nm) contributes more to phosphorescence than fluorescence, implying stronger intersystem crossing (ISC) for highly excited singlet states. Theoretical...

ReaxFF molecular dynamics simulations on lithium sulfur batteries

Understanding of the structural, and kinetic behavior of the sulfur cathode materials are crucial for designing high performance Li-S batteries. In a recent study, ReaxFF molecular dynamics simulations has been utilized to study sulfur cathode...