DFT Mechanistic Study of the Selective Terminal C-H Activation of n-Pentane with a Tungsten Allyl Nitrosyl Complex

Handle URI:
http://hdl.handle.net/10754/622706
Title:
DFT Mechanistic Study of the Selective Terminal C-H Activation of n-Pentane with a Tungsten Allyl Nitrosyl Complex
Authors:
Lee, Richmond; Tan, Davin; Liu, Chaoli; Li, Huaifeng ( 0000-0001-9661-803X ) ; Guo, Hao; Shyue, Jing-Jong; Huang, Kuo-Wei ( 0000-0003-1900-2658 )
Abstract:
Mechanistic insights into the selective C-H terminal activation of n-pentane with tungsten allyl nitrosyl complex reported by Legzdins were gained by employing density functional theory with B3LYP hybrid functional. Using Bader’s atom in molecules (AIM) analysis on the elementary steps of the hydrogen transfer process, TS1 and TS2, it was observed that the calculated H-transfer models were closely similar to Hall’s metal-assisted σ-bond metathesis through bond critical point (BCP) comparisons. One distinguishable feature was the fact that the formal oxidation state of the W changed in the concerted H-transfer process. To better differentiate, we term these processes as ‘Formal Reductive Hydrogen Transfer’ (FRHT) for TS1 and ‘Formal Oxidative Hydrogen Transfer’ (FOHT) for TS2.
KAUST Department:
KAUST Catalysis Center (KCC); Physical Sciences and Engineering (PSE) Division
Citation:
Lee R, Tan D, Liu C, Li H, Guo H, et al. (2017) DFT Mechanistic Study of the Selective Terminal C-H Activation of n-Pentane with a Tungsten Allyl Nitrosyl Complex. Journal of Saudi Chemical Society. Available: http://dx.doi.org/10.1016/j.jscs.2016.12.004.
Publisher:
Elsevier BV
Journal:
Journal of Saudi Chemical Society
Issue Date:
17-Jan-2017
DOI:
10.1016/j.jscs.2016.12.004
Type:
Article
ISSN:
1319-6103
Sponsors:
This work is supported by King Abdullah University of Science and Technology. Additional computing time from KAUST scientific cluster (Noor) and scholarships to R. Lee, D.Tan, and H.-F. Li are gratefully acknowledged.
Additional Links:
http://www.sciencedirect.com/science/article/pii/S1319610317300017
Appears in Collections:
Articles; Physical Sciences and Engineering (PSE) Division; KAUST Catalysis Center (KCC)

Full metadata record

DC FieldValue Language
dc.contributor.authorLee, Richmonden
dc.contributor.authorTan, Davinen
dc.contributor.authorLiu, Chaolien
dc.contributor.authorLi, Huaifengen
dc.contributor.authorGuo, Haoen
dc.contributor.authorShyue, Jing-Jongen
dc.contributor.authorHuang, Kuo-Weien
dc.date.accessioned2017-01-22T10:45:41Z-
dc.date.available2017-01-22T10:45:41Z-
dc.date.issued2017-01-17en
dc.identifier.citationLee R, Tan D, Liu C, Li H, Guo H, et al. (2017) DFT Mechanistic Study of the Selective Terminal C-H Activation of n-Pentane with a Tungsten Allyl Nitrosyl Complex. Journal of Saudi Chemical Society. Available: http://dx.doi.org/10.1016/j.jscs.2016.12.004.en
dc.identifier.issn1319-6103en
dc.identifier.doi10.1016/j.jscs.2016.12.004en
dc.identifier.urihttp://hdl.handle.net/10754/622706-
dc.description.abstractMechanistic insights into the selective C-H terminal activation of n-pentane with tungsten allyl nitrosyl complex reported by Legzdins were gained by employing density functional theory with B3LYP hybrid functional. Using Bader’s atom in molecules (AIM) analysis on the elementary steps of the hydrogen transfer process, TS1 and TS2, it was observed that the calculated H-transfer models were closely similar to Hall’s metal-assisted σ-bond metathesis through bond critical point (BCP) comparisons. One distinguishable feature was the fact that the formal oxidation state of the W changed in the concerted H-transfer process. To better differentiate, we term these processes as ‘Formal Reductive Hydrogen Transfer’ (FRHT) for TS1 and ‘Formal Oxidative Hydrogen Transfer’ (FOHT) for TS2.en
dc.description.sponsorshipThis work is supported by King Abdullah University of Science and Technology. Additional computing time from KAUST scientific cluster (Noor) and scholarships to R. Lee, D.Tan, and H.-F. Li are gratefully acknowledged.en
dc.publisherElsevier BVen
dc.relation.urlhttp://www.sciencedirect.com/science/article/pii/S1319610317300017en
dc.rights© 2017. This manuscript version is made available under the CC-BY-NC-ND 4.0 license http://creativecommons.org/licenses/by-nc-nd/4.0/en
dc.rights.urihttps://creativecommons.org/licenses/by-nc-nd/4.0/en
dc.subjectTungstenen
dc.subjectDFTen
dc.subjectC-H bond activationen
dc.subjectnitrosyl complexen
dc.titleDFT Mechanistic Study of the Selective Terminal C-H Activation of n-Pentane with a Tungsten Allyl Nitrosyl Complexen
dc.typeArticleen
dc.contributor.departmentKAUST Catalysis Center (KCC)en
dc.contributor.departmentPhysical Sciences and Engineering (PSE) Divisionen
dc.identifier.journalJournal of Saudi Chemical Societyen
dc.eprint.versionPost-printen
dc.contributor.institutionDepartment of chemistry, Fudan University, 220 Handan Road, Shanghai, 200433, PR Chinaen
dc.contributor.institutionResearch Center of Applied Sciences, Academia Sinica, 128 Academia Rd., Sec. 2, Nankang, Taipei 115, Taiwanen
kaust.authorLee, Richmonden
kaust.authorTan, Davinen
kaust.authorLiu, Chaolien
kaust.authorLi, Huaifengen
kaust.authorHuang, Kuo-Weien
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