Publication:
Insight into the Thiol-yne Kinetics via a Computational Approach

dc.contributor.authorERDEM, SAFİYE
dc.contributor.authorsFindik, Volkan; Varinca, Betul Tuba; Degirmenci, Isa; Erdem, Safiye Sag
dc.date.accessioned2022-03-12T22:57:58Z
dc.date.available2022-03-12T22:57:58Z
dc.date.issued2021
dc.description.abstractThiol-yne reactions have drawn attention because of the click nature as well as the regular step-growth network nature of their products, despite the radical-mediated reactant. However, the factors governing the reaction pathways have not been examined using quantum chemical tools in a comprehensive manner. Thereupon, we have systematically investigated the mechanism of thiol-yne reactions, focusing on the structural influences of thiol and alkyne functionalities. The reaction kinetics, structure-reactivity relations, and E/Z diastereoselectivity of the products have been enlightened for the first cycle of the thiol-yne polymerization reaction. For this reason, a diverse set of 11 thiol-yne reactions with four thiols and eight alkynes was modeled by means of density functional theory. We performed a benchmark study and determined the M06-2X/6-31+G(d,p) level of theory as the best cost-effective methodology to model such reactions. Results reveal that spin density, the stabilities of sulfur radicals for propagation, and the stability of alkenyl intermediate radicals for the chain transfer are the determining factors of each reaction rate. Intramolecular p-p stacking interactions at transition-state structures are found to be responsible for Z diastereoselectivity.
dc.identifier.doi10.1021/acs.jpca.0c11599
dc.identifier.eissn1520-5215
dc.identifier.issn1089-5639
dc.identifier.pubmed33887139
dc.identifier.urihttps://hdl.handle.net/11424/237123
dc.identifier.wosWOS:000648873600004
dc.language.isoeng
dc.publisherAMER CHEMICAL SOC
dc.relation.ispartofJOURNAL OF PHYSICAL CHEMISTRY A
dc.rightsinfo:eu-repo/semantics/closedAccess
dc.subjectFREE-RADICAL POLYMERIZATION
dc.subjectCLICK CHEMISTRY
dc.subjectBENZENETHIYL RADICALS
dc.subjectTHIOLACETIC ACID
dc.subjectANTI-MARKOVNIKOV
dc.subjectFLASH-PHOTOLYSIS
dc.subjectADDITION RATES
dc.subjectTHIYL RADICALS
dc.subjectENE
dc.subjectMECHANISM
dc.titleInsight into the Thiol-yne Kinetics via a Computational Approach
dc.typearticle
dspace.entity.typePublication
local.avesis.id52330dfd-be52-473f-9a71-b785be5f4465
local.import.packageSS17
local.indexed.atWOS
local.indexed.atSCOPUS
local.indexed.atPUBMED
local.journal.numberofpages13
oaire.citation.endPage3568
oaire.citation.issue17
oaire.citation.startPage3556
oaire.citation.titleJOURNAL OF PHYSICAL CHEMISTRY A
oaire.citation.volume125
relation.isAuthorOfPublication99f2f09c-7e48-402f-9bb9-ccdd73c27ec2
relation.isAuthorOfPublication.latestForDiscovery99f2f09c-7e48-402f-9bb9-ccdd73c27ec2

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