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dc.contributor.authorMunkerup, Kristin
dc.contributor.authorThulin, Michael
dc.contributor.authorTan, Davin
dc.contributor.authorLim, XiaoZhi
dc.contributor.authorLee, Richmond
dc.contributor.authorHuang, Kuo-Wei
dc.date.accessioned2019-09-10T13:06:22Z
dc.date.available2019-09-10T13:06:22Z
dc.date.issued2019-08-06
dc.identifier.citationMunkerup, K., Thulin, M., Tan, D., Lim, X., Lee, R., & Huang, K.-W. (2019). Importance of thorough conformational analysis in modelling transition metal-mediated reactions: Case studies on pincer complexes containing phosphine groups. Journal of Saudi Chemical Society, 23(8), 1206–1218. doi:10.1016/j.jscs.2019.07.005
dc.identifier.doi10.1016/j.jscs.2019.07.005
dc.identifier.urihttp://hdl.handle.net/10754/656719
dc.description.abstractAdvances in processing capabilities of computer clusters have allowed for the full modeling of organometallic complexes that previously would have been simplified to reduce computational cost. Increased feasibility of computational modeling offers new challenges, not only in terms of limitations of methods and theory, but attention should be paid to complexes that can exist in many conformations, as the appropriate choice of conformer may be easily overlooked. In this work a series of pincer complexes with isopropyl and cyclopentyl substituents have been chosen as examples to demonstrate the importance of conformational analysis. The complexes examined contain four isopropyl or cyclopentyl groups on phosphor atoms generating between 27 and 324 possible rotamers. The importance of conformational search in a mechanistic investigation is demonstrated with the CO2 insertion into a nickel hydride bond of POCOP iPr nickel hydride complex. Results show that the reaction energy profile can be both exergonic and endergonic depending on rotamer choice. Specifically, the POCOPi Pr Ni-formato complex product of the CO2 insertion reaction had an energy difference between the lowest and highest energy rotamer as high as 16.8 kcal/mol. The significant energy differences between rotamers highlight the importance of thorough conformational analysis and should be taken into consideration when evaluating the energy profile of related reactions.
dc.description.sponsorshipThe authors acknowledge the service of Ibex and Shaheen 2 High Performance Computing Facilities and financial support from King Abdullah University of Science and Technology (KAUST).
dc.publisherElsevier B.V.
dc.relation.urlhttps://linkinghub.elsevier.com/retrieve/pii/S131961031930078X
dc.rightsNOTICE: this is the author’s version of a work that was accepted for publication in Journal of Saudi Chemical Society. Changes resulting from the publishing process, such as peer review, editing, corrections, structural formatting, and other quality control mechanisms may not be reflected in this document. Changes may have been made to this work since it was submitted for publication. A definitive version was subsequently published in Journal of Saudi Chemical Society, [[Volume], [Issue], (2019-01-01)] DOI: 10.1016/j.jscs.2019.07.005 . © 2019. This manuscript version is made available under the CC-BY-NC-ND 4.0 license http://creativecommons.org/licenses/by-nc-nd/4.0/
dc.subjectConformational analysis
dc.subjectPincer
dc.subjectMechanism
dc.subjectRotamers
dc.subjectDFT
dc.titleImportance of thorough conformational analysis in modelling transition metal-mediated reactions: Case studies on pincer complexes containing phosphine groups
dc.typeArticle
dc.contributor.departmentChemical Science Program
dc.contributor.departmentHomogeneous Catalysis Laboratory (HCL)
dc.contributor.departmentKAUST Catalysis Center (KCC)
dc.contributor.departmentPhysical Science and Engineering (PSE) Division
dc.identifier.journalJournal of Saudi Chemical Society
dc.eprint.versionPost-print
dc.contributor.institutionDeparment of Computer Science, University of Copenhagen, Universitetsparken 1, 2100 Copenhagen Ø, Denmark
kaust.personMunkerup, Kristin
kaust.personTan, Davin
kaust.personLim, XiaoZhi
kaust.personLee, Richmond
kaust.personHuang, Kuo-Wei
refterms.dateFOA2019-09-10T13:07:36Z
kaust.acknowledged.supportUnitIbex
kaust.acknowledged.supportUnitShaheen 2 High Performance Computing Facilities
dc.date.published-online2019-08-06
dc.date.published-print2019-08


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