1,2-CF bond activation of perfluoroarenes and alkylidene isomers of titanium. DFT analysis of the C-F bond activation pathway and rotation of the titanium alkylidene moiety

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dc.contributor.authorAndino, Jose G.ko
dc.contributor.authorFan, Hongjunko
dc.contributor.authorFout, Alison R.ko
dc.contributor.authorBailey, Brad C.ko
dc.contributor.authorBaik, Mu-Hyunko
dc.contributor.authorMindiola, Daniel J.ko
dc.date.accessioned2016-04-12T07:36:16Z-
dc.date.available2016-04-12T07:36:16Z-
dc.date.created2015-09-11-
dc.date.created2015-09-11-
dc.date.issued2011-12-
dc.identifier.citationJOURNAL OF ORGANOMETALLIC CHEMISTRY, v.696, no.25, pp.4138 - 4146-
dc.identifier.issn0022-328X-
dc.identifier.urihttp://hdl.handle.net/10203/203305-
dc.description.abstractIsomeric alkylidene complexes syn- and anti-(PNP)Ti=[C(t)Bu(C(6)F(5))](F) (1) and (PNP)Ti=[C(t)Bu(C(7)F(7))](F) (2) have been generated from C-F bond addition of hexafluorobenzene (C(6)F(6)) and octafluorotoluene (C(7)F(8)) across the alkylidyne ligand of transient (PNP)Ti=C(t)Bu (A) (PNP(-)=N[2-P(CHMe(2))(2)-4-methylphenyl](2)), which was generated from the precursor (PNP)Ti=CH(t)Bu(CH(t)(2)Bu). Two mechanistic scenarios for the activation of the C-F bond by A are considered: 1,2-CF addition and [2 + 2]-cycloaddition/beta-fluoride elimination. Upon formation of the alkylidenes 1 and 2, the kinetic and thermodynamic alkylidene product is the syn isomer, which gradually isomerizes to the corresponding anti isomer to ultimately establish an equilibrium mixture (when using 1, 65/35) if the solution is heated in benzene to 105 degrees C for 1 h. Single crystal X-Ray crystallographic data obtained for the two isomers of 2 (and syn isomer of 1) are in good agreement with computed DFT-optimized models. Our calculations suggest convincingly that the isomerization process proceeds via a concerted rotation involving a heterolytic bond cleavage about the alkylidene bond. The two rotamers are thermodynamically very close in energy and interconvert with an estimated barrier of similar to 26 kcal/mol. The electronic reason for this unexpectedly low barrier is investigated. (C) 2011 Elsevier B.V. All rights reserved.-
dc.languageEnglish-
dc.publisherELSEVIER SCIENCE SA-
dc.subjectEFFECTIVE CORE POTENTIALS-
dc.subjectRING-OPENING METATHESIS-
dc.subjectMOLECULAR CALCULATIONS-
dc.subjectMULTIPLE BONDS-
dc.subjectTIC LINKAGE-
dc.subjectEXCHANGE-
dc.subjectDENSITY-
dc.subjectDENITROGENATION-
dc.subjectREACTIVITY-
dc.subjectCOMPLEXES-
dc.title1,2-CF bond activation of perfluoroarenes and alkylidene isomers of titanium. DFT analysis of the C-F bond activation pathway and rotation of the titanium alkylidene moiety-
dc.typeArticle-
dc.identifier.wosid000297152600032-
dc.identifier.scopusid2-s2.0-81355148910-
dc.type.rimsART-
dc.citation.volume696-
dc.citation.issue25-
dc.citation.beginningpage4138-
dc.citation.endingpage4146-
dc.citation.publicationnameJOURNAL OF ORGANOMETALLIC CHEMISTRY-
dc.identifier.doi10.1016/j.jorganchem.2011.07.037-
dc.contributor.localauthorBaik, Mu-Hyun-
dc.contributor.nonIdAuthorAndino, Jose G.-
dc.contributor.nonIdAuthorFan, Hongjun-
dc.contributor.nonIdAuthorFout, Alison R.-
dc.contributor.nonIdAuthorBailey, Brad C.-
dc.contributor.nonIdAuthorMindiola, Daniel J.-
dc.type.journalArticleArticle-
dc.subject.keywordAuthorAlkylidene-
dc.subject.keywordAuthorTitanium-
dc.subject.keywordAuthorC-F bond activation-
dc.subject.keywordAuthor1,2-CF bond addition-
dc.subject.keywordAuthorRotation-
dc.subject.keywordPlusEFFECTIVE CORE POTENTIALS-
dc.subject.keywordPlusRING-OPENING METATHESIS-
dc.subject.keywordPlusMOLECULAR CALCULATIONS-
dc.subject.keywordPlusMULTIPLE BONDS-
dc.subject.keywordPlusTIC LINKAGE-
dc.subject.keywordPlusEXCHANGE-
dc.subject.keywordPlusDENSITY-
dc.subject.keywordPlusDENITROGENATION-
dc.subject.keywordPlusREACTIVITY-
dc.subject.keywordPlusCOMPLEXES-
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