DC Field | Value | Language |
---|---|---|
dc.contributor.author | Andino, Jose G. | ko |
dc.contributor.author | Fan, Hongjun | ko |
dc.contributor.author | Fout, Alison R. | ko |
dc.contributor.author | Bailey, Brad C. | ko |
dc.contributor.author | Baik, Mu-Hyun | ko |
dc.contributor.author | Mindiola, Daniel J. | ko |
dc.date.accessioned | 2016-04-12T07:36:16Z | - |
dc.date.available | 2016-04-12T07:36:16Z | - |
dc.date.created | 2015-09-11 | - |
dc.date.created | 2015-09-11 | - |
dc.date.issued | 2011-12 | - |
dc.identifier.citation | JOURNAL OF ORGANOMETALLIC CHEMISTRY, v.696, no.25, pp.4138 - 4146 | - |
dc.identifier.issn | 0022-328X | - |
dc.identifier.uri | http://hdl.handle.net/10203/203305 | - |
dc.description.abstract | Isomeric 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.language | English | - |
dc.publisher | ELSEVIER SCIENCE SA | - |
dc.subject | EFFECTIVE CORE POTENTIALS | - |
dc.subject | RING-OPENING METATHESIS | - |
dc.subject | MOLECULAR CALCULATIONS | - |
dc.subject | MULTIPLE BONDS | - |
dc.subject | TIC LINKAGE | - |
dc.subject | EXCHANGE | - |
dc.subject | DENSITY | - |
dc.subject | DENITROGENATION | - |
dc.subject | REACTIVITY | - |
dc.subject | COMPLEXES | - |
dc.title | 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 | - |
dc.type | Article | - |
dc.identifier.wosid | 000297152600032 | - |
dc.identifier.scopusid | 2-s2.0-81355148910 | - |
dc.type.rims | ART | - |
dc.citation.volume | 696 | - |
dc.citation.issue | 25 | - |
dc.citation.beginningpage | 4138 | - |
dc.citation.endingpage | 4146 | - |
dc.citation.publicationname | JOURNAL OF ORGANOMETALLIC CHEMISTRY | - |
dc.identifier.doi | 10.1016/j.jorganchem.2011.07.037 | - |
dc.contributor.localauthor | Baik, Mu-Hyun | - |
dc.contributor.nonIdAuthor | Andino, Jose G. | - |
dc.contributor.nonIdAuthor | Fan, Hongjun | - |
dc.contributor.nonIdAuthor | Fout, Alison R. | - |
dc.contributor.nonIdAuthor | Bailey, Brad C. | - |
dc.contributor.nonIdAuthor | Mindiola, Daniel J. | - |
dc.type.journalArticle | Article | - |
dc.subject.keywordAuthor | Alkylidene | - |
dc.subject.keywordAuthor | Titanium | - |
dc.subject.keywordAuthor | C-F bond activation | - |
dc.subject.keywordAuthor | 1,2-CF bond addition | - |
dc.subject.keywordAuthor | Rotation | - |
dc.subject.keywordPlus | EFFECTIVE CORE POTENTIALS | - |
dc.subject.keywordPlus | RING-OPENING METATHESIS | - |
dc.subject.keywordPlus | MOLECULAR CALCULATIONS | - |
dc.subject.keywordPlus | MULTIPLE BONDS | - |
dc.subject.keywordPlus | TIC LINKAGE | - |
dc.subject.keywordPlus | EXCHANGE | - |
dc.subject.keywordPlus | DENSITY | - |
dc.subject.keywordPlus | DENITROGENATION | - |
dc.subject.keywordPlus | REACTIVITY | - |
dc.subject.keywordPlus | COMPLEXES | - |
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