Mechanistic Analysis of Alkyne Haloboration: A DFT, MP2, and DLPNO-CCSD(T) Study
The result's identifiers
Result code in 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>
Result on the web
<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>
Alternative languages
Result language
angličtina
Original language name
Mechanistic Analysis of Alkyne Haloboration: A DFT, MP2, and DLPNO-CCSD(T) Study
Original language description
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.
Czech name
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Czech description
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Classification
Type
J<sub>imp</sub> - Article in a specialist periodical, which is included in the Web of Science database
CEP classification
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OECD FORD branch
10403 - Physical chemistry
Result continuities
Project
Result was created during the realization of more than one project. More information in the Projects tab.
Continuities
P - Projekt vyzkumu a vyvoje financovany z verejnych zdroju (s odkazem do CEP)<br>I - Institucionalni podpora na dlouhodoby koncepcni rozvoj vyzkumne organizace
Others
Publication year
2023
Confidentiality
S - Úplné a pravdivé údaje o projektu nepodléhají ochraně podle zvláštních právních předpisů
Data specific for result type
Name of the periodical
Journal of Physical Chemistry A
ISSN
1089-5639
e-ISSN
1520-5215
Volume of the periodical
127
Issue of the periodical within the volume
30
Country of publishing house
US - UNITED STATES
Number of pages
12
Pages from-to
6135-6146
UT code for WoS article
001035689000001
EID of the result in the Scopus database
2-s2.0-85166442534