Theoretical Insight on the Formation Mechanism of a Trisubstituted Derivative of Closo-Decaborate Anion [B10H7O2CCH3(NCCH3)]0 DOI Creative Commons
I. N. Klyukin, Anastasia V. Kolbunova, Alexander S. Novikov

et al.

Inorganics, Journal Year: 2023, Volume and Issue: 11(5), P. 201 - 201

Published: May 6, 2023

A theoretical modelling of the interaction process between a protonated complex carboxonium derivative [2,6-B10H8O2CCH3*Hfac]0 and acetonitrile molecule CH3CN was carried out. As result process, trisubstituted [B10H7O2CCH3(NCCH3)]0 formed. This reaction has an electrophile-induced nucleophilic substitution (EINS) mechanism. The main intermediates transition states were established. in case all previously investigated EINS processes, key intermediate anion with dihydrogen H2 fragment attached to one boron atom (B(H2) structure motif). can proceed on different position cluster cage. potential pathways assessed. It established that B4 cage most energetically favourable, [2,4,6-B10H7O2CCH3(NCCH3)]0 isomer

Language: Английский

State-of-the-art local correlation methods enable affordable gold standard quantum chemistry for up to hundreds of atoms DOI Creative Commons
Péter R. Nagy

Chemical Science, Journal Year: 2024, Volume and Issue: 15(36), P. 14556 - 14584

Published: Jan. 1, 2024

In this feature, we review the current capabilities of local electron correlation methods up to coupled cluster model with single, double, and perturbative triple excitations [CCSD(T)], which is a gold standard in quantum chemistry. The main computational aspects method types are assessed from perspective applications, but focus kept on how achieve chemical accuracy (

Language: Английский

Citations

11
Mechanism of the Visible-Light-Promoted C(sp3)–H Oxidation via Uranyl Photocatalysis DOI

Shuyun Zhang,

S. H. Tang,

Yanxin Jiang

et al.

Inorganic Chemistry, Journal Year: 2024, Volume and Issue: 63(5), P. 2418 - 2430

Published: Jan. 24, 2024

Uranyl cation, as an emerging photocatalyst, has been successfully applied to synthetic chemistry in recent years and displayed remarkable catalytic ability under visible light. However, the molecular-level reaction mechanisms of uranyl photocatalysis are unclear. Here, we explore mechanism stepwise benzylic C-H oxygenation typical alkyl-substituted aromatics (i.e., toluene, ethylbenzene, cumene) via using theoretical experimental methods. Theoretical calculation results show that most favorable path for photocatalytic oxidation is follows: first, hydrogen atom transfer (HAT) from benzyl position form a carbon radical ([R

Language: Английский

Citations

8
Theoretical Insight on the Formation Mechanism of a Trisubstituted Derivative of Closo-Decaborate Anion [B10H7O2CCH3(NCCH3)]0 DOI Creative Commons
I. N. Klyukin, Anastasia V. Kolbunova, Alexander S. Novikov

et al.

Inorganics, Journal Year: 2023, Volume and Issue: 11(5), P. 201 - 201

Published: May 6, 2023

A theoretical modelling of the interaction process between a protonated complex carboxonium derivative [2,6-B10H8O2CCH3*Hfac]0 and acetonitrile molecule CH3CN was carried out. As result process, trisubstituted [B10H7O2CCH3(NCCH3)]0 formed. This reaction has an electrophile-induced nucleophilic substitution (EINS) mechanism. The main intermediates transition states were established. in case all previously investigated EINS processes, key intermediate anion with dihydrogen H2 fragment attached to one boron atom (B(H2) structure motif). can proceed on different position cluster cage. potential pathways assessed. It established that B4 cage most energetically favourable, [2,4,6-B10H7O2CCH3(NCCH3)]0 isomer

Language: Английский

Citations

3