Mechanistic Analysis of Alkyne Haloboration: A DFT, MP2, and DLPNO-CCSD(T) Study

Kód výsledku v IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F00216224%3A14310%2F23%3A00131314" target="_blank" >RIV/00216224:14310/23:00131314 - isvavai.cz</a>

Výsledek na webu

<a href="https://doi.org/10.1021/acs.jpca.3c00607" target="_blank" >https://doi.org/10.1021/acs.jpca.3c00607</a>

DOI - Digital Object Identifier

<a href="http://dx.doi.org/10.1021/acs.jpca.3c00607" target="_blank" >10.1021/acs.jpca.3c00607</a>

Jazyk výsledku

angličtina

Název v původním jazyce

Mechanistic Analysis of Alkyne Haloboration: A DFT, MP2, and DLPNO-CCSD(T) Study

Popis výsledku v původním jazyce

Stereocontrol of the alkyne haloboration reaction has received attention in many experimental but few theoretical studies. Here we present a detailed quantum-chemical study of mechanisms leading to Z versus E isomers of haloboration products, considering acetylene and propyne combined with BCl3, BBr3, and BI3. Calculations using B3LYP-D3, MP2, and DLPNO-CCSD(T) methods are used to study polar reactions between the alkyne and BX3 in the absence and presence of an additional halide anion whose content in the reaction mixture can be controlled experimentally. The formation of anti-haloboration products via radical mechanisms is also explored, namely, by adding BX3 to (Z)-halovinyl radical. For the anti-haloboration of propyne, the radical route is prohibited by the regiochemistry of the initiating halopropenyl radical, while the polar route is unlikely due to a competitive allene generation. In contrast, energetically accessible routes exist for both syn- and anti-bromoboration of acetylene; hence, careful control of reaction conditions is necessary to steer the stereochemical outcome. Methodologically, MP2 results correspond better to the DLPNO-CCSD(T) energies than the B3LYP-D3 results in terms of both reaction barrier heights and relative ordering of energetically close stationary points.

Název v anglickém jazyce

Mechanistic Analysis of Alkyne Haloboration: A DFT, MP2, and DLPNO-CCSD(T) Study

Popis výsledku anglicky

Stereocontrol of the alkyne haloboration reaction has received attention in many experimental but few theoretical studies. Here we present a detailed quantum-chemical study of mechanisms leading to Z versus E isomers of haloboration products, considering acetylene and propyne combined with BCl3, BBr3, and BI3. Calculations using B3LYP-D3, MP2, and DLPNO-CCSD(T) methods are used to study polar reactions between the alkyne and BX3 in the absence and presence of an additional halide anion whose content in the reaction mixture can be controlled experimentally. The formation of anti-haloboration products via radical mechanisms is also explored, namely, by adding BX3 to (Z)-halovinyl radical. For the anti-haloboration of propyne, the radical route is prohibited by the regiochemistry of the initiating halopropenyl radical, while the polar route is unlikely due to a competitive allene generation. In contrast, energetically accessible routes exist for both syn- and anti-bromoboration of acetylene; hence, careful control of reaction conditions is necessary to steer the stereochemical outcome. Methodologically, MP2 results correspond better to the DLPNO-CCSD(T) energies than the B3LYP-D3 results in terms of both reaction barrier heights and relative ordering of energetically close stationary points.

Druh

J_imp - Článek v periodiku v databázi Web of Science

CEP obor

—

OECD FORD obor

10403 - Physical chemistry

Projekt

Výsledek vznikl pri realizaci vícero projektů. Více informací v záložce Projekty.

Návaznosti

P - Projekt vyzkumu a vyvoje financovany z verejnych zdroju (s odkazem do CEP)<br>I - Institucionalni podpora na dlouhodoby koncepcni rozvoj vyzkumne organizace

Rok uplatnění

2023

Kód důvěrnosti údajů

S - Úplné a pravdivé údaje o projektu nepodléhají ochraně podle zvláštních právních předpisů

Název periodika

Journal of Physical Chemistry A

ISSN

1089-5639

e-ISSN

1520-5215

Svazek periodika

127

Číslo periodika v rámci svazku

30

Stát vydavatele periodika

US - Spojené státy americké

Počet stran výsledku

12

Strana od-do

6135-6146

Kód UT WoS článku

001035689000001

EID výsledku v databázi Scopus

2-s2.0-85166442534