DC Field | Value | Language |
---|---|---|
dc.contributor.author | Churchill, David G | ko |
dc.contributor.author | Bridgewater, BM | ko |
dc.contributor.author | Zhu, G | ko |
dc.contributor.author | Pang, KL | ko |
dc.contributor.author | Parkin, G | ko |
dc.date.accessioned | 2013-03-07T17:56:09Z | - |
dc.date.available | 2013-03-07T17:56:09Z | - |
dc.date.created | 2012-02-06 | - |
dc.date.created | 2012-02-06 | - |
dc.date.issued | 2006-01 | - |
dc.identifier.citation | POLYHEDRON, v.25, no.2, pp.499 - 512 | - |
dc.identifier.issn | 0277-5387 | - |
dc.identifier.uri | http://hdl.handle.net/10203/90843 | - |
dc.description.abstract | [Me2Si(C5Me4)(2)]MoH2 reacts with furan and benzofuran to yield products resulting from C-H bond cleavage, namely [Me2Si(C5Me4)(2)]Mo(eta(1)-C-C4H3O)H and [Me2Si(C5Me4)(2)]Mo(eta(2)-C-C8H5O)H, whereas the corresponding reactions of selenophene and benzoselenophene yield products resulting from C-Se bond cleavage, namely [Me2Si(C5Me4)(2)]Mo(eta(2)-C,Se-SeC4H4) and [Me2Si(C5Me4)(2)]Mo(eta(2)-C,Se-SeC8H6). On this basis, the reactivity of the selenophene derivatives is analogous to that of previously reported thiophene derivatives, while the reactivity of the furan derivatives is unique. DFT calculations indicate that C-E (E = O, S, Se) bond cleavage is thermodynamically more favored than C-H bond cleavage for each of the chalcogen derivatives. As such, the calculations provide evidence that C-O bond cleavage of the furan derivatives is not observed because of kinetic factors. DFT calculations also demonstrate that the observation of C-S bond cleavage of thiophene by the ansa metallocene [Me2Si(C5Me4)(2)]MoH2 and C-H bond cleavage by Cp2MoH2 is dictated by thermodynamic factors. Specifically, the Me2Si ansa bridge thermodynamically favors [Me2Si(C5Me4)(2)]Mo(eta(2)-C,S-SC4H4) over [Me2Si(C5Me4)(2)]Mo(eta(1)-C-SC4H3)H because the bridge promotes a shift in the coordination of the cyclopentadienyl rings from eta(5)-coordination towards eta(3)-coordination and this thermodynamically unfavorable modification is stabilized by sulfur-to-metal pi-donation within [Me2Si(C5Me4)(2)]Mo(eta(2)-C,S-SC4H4). (c) 2005 Elsevier Ltd. All rights reserved. | - |
dc.language | English | - |
dc.publisher | PERGAMON-ELSEVIER SCIENCE LTD | - |
dc.subject | TRANSITION-METAL-COMPLEXES | - |
dc.subject | C-S BONDS | - |
dc.subject | OXIDATIVE ADDITION-REACTIONS | - |
dc.subject | IRIDIUM PHOSPHINE CHEMISTRY | - |
dc.subject | SULFUR BOND | - |
dc.subject | HYDRODESULFURIZATION REACTION | - |
dc.subject | HOMOGENEOUS HYDRODESULFURIZATION | - |
dc.subject | DEEP HYDRODESULFURIZATION | - |
dc.subject | CRYSTAL-STRUCTURE | - |
dc.subject | ORGANOMETALLIC COMPLEXES | - |
dc.title | Carbon-hydrogen versus carbon-chalcogen bond cleavage of furan, thiophene and selenophene by ansa molybdenocene complexes | - |
dc.type | Article | - |
dc.identifier.wosid | 000234928500035 | - |
dc.identifier.scopusid | 2-s2.0-30144440930 | - |
dc.type.rims | ART | - |
dc.citation.volume | 25 | - |
dc.citation.issue | 2 | - |
dc.citation.beginningpage | 499 | - |
dc.citation.endingpage | 512 | - |
dc.citation.publicationname | POLYHEDRON | - |
dc.identifier.doi | 10.1016/j.poly.2005.08.016 | - |
dc.contributor.localauthor | Churchill, David G | - |
dc.contributor.nonIdAuthor | Bridgewater, BM | - |
dc.contributor.nonIdAuthor | Zhu, G | - |
dc.contributor.nonIdAuthor | Pang, KL | - |
dc.contributor.nonIdAuthor | Parkin, G | - |
dc.type.journalArticle | Review | - |
dc.subject.keywordAuthor | molybdenum | - |
dc.subject.keywordAuthor | hydrodesulfurization | - |
dc.subject.keywordAuthor | hydrodenitrogenation | - |
dc.subject.keywordAuthor | ansa metallocene | - |
dc.subject.keywordAuthor | furan | - |
dc.subject.keywordAuthor | thiophene | - |
dc.subject.keywordAuthor | seleneophen | - |
dc.subject.keywordPlus | TRANSITION-METAL-COMPLEXES | - |
dc.subject.keywordPlus | C-S BONDS | - |
dc.subject.keywordPlus | OXIDATIVE ADDITION-REACTIONS | - |
dc.subject.keywordPlus | IRIDIUM PHOSPHINE CHEMISTRY | - |
dc.subject.keywordPlus | SULFUR BOND | - |
dc.subject.keywordPlus | HYDRODESULFURIZATION REACTION | - |
dc.subject.keywordPlus | HOMOGENEOUS HYDRODESULFURIZATION | - |
dc.subject.keywordPlus | DEEP HYDRODESULFURIZATION | - |
dc.subject.keywordPlus | CRYSTAL-STRUCTURE | - |
dc.subject.keywordPlus | ORGANOMETALLIC COMPLEXES | - |
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