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Article: C-H bond activation by a hydrotris(pyrazolyl)borato ruthenium hydride complex

TitleC-H bond activation by a hydrotris(pyrazolyl)borato ruthenium hydride complex
Authors
Issue Date2003
PublisherAmerican Chemical Society. The Journal's web site is located at http://pubs.acs.org/organometallics
Citation
Organometallics, 2003, v. 22 n. 4, p. 641-651 How to Cite?
AbstractThe ruthenium complex TpRu(PPh 3)(CH 3CN)H (Tp = hydrotris(pyrazolyl)borate) catalyzes H/D exchange between CH 4 and some deuterated organic solvents-benzene-d 6, tetrahydrofuran-d 8, diethyl ether-d 10, and dioxane-d 8. Preferential cleavage of the α-C-D and the β-C-D bonds of THF-d 8 and diethyl ether-d 10, respectively, is observed. The H/D exchange processes have been investigated by density functional theory calculations at the B3LYP level. Theoretical study on the reaction mechanism suggests that σ-complexes TpRu(PPh 3)(η 2-H-R)H are active species in the exchange processes. During the exchange processes, the reversible transformations of TpRu(PPh 3)(η 2-H-R)H to TpRu(PPh 3)(η 2-H 2)R are the crucial steps. The barriers for the transformations are in the range 10-13.4 kcal/mol. Interestingly, the transition states for the transformations correspond to the seven-coordinate TpRu(PPh 3)(R)(H)(H), which are species derived from the oxidative addition of H-R to the metal center. The exchange processes involve transformations of the (η 2-H-R) species to the (η 2-H 2) species followed by H-H rotation in the latter. The rotation barriers are calculated to be in the range 2-4 kcal/mol. The exchange process having an aromatic R group is found to be most favorable due to the strong Ru-C(sp 2) bonding, which stabilizes the (η 2-H 2) species and lowers the transformation barrier. The complex TpRu(PPh 3)(CH 3CN)H catalyzes H/D exchange between H 2 and the deuterated solvents too.
Persistent Identifierhttp://hdl.handle.net/10722/167786
ISSN
2014 Impact Factor: 4.126
ISI Accession Number ID
References

 

DC FieldValueLanguage
dc.contributor.authorNg, SMen_US
dc.contributor.authorLam, WHen_US
dc.contributor.authorMak, CCen_US
dc.contributor.authorTsang, CWen_US
dc.contributor.authorJia, Gen_US
dc.contributor.authorLin, Zen_US
dc.contributor.authorLau, CPen_US
dc.date.accessioned2012-10-08T03:11:35Z-
dc.date.available2012-10-08T03:11:35Z-
dc.date.issued2003en_US
dc.identifier.citationOrganometallics, 2003, v. 22 n. 4, p. 641-651en_US
dc.identifier.issn0276-7333en_US
dc.identifier.urihttp://hdl.handle.net/10722/167786-
dc.description.abstractThe ruthenium complex TpRu(PPh 3)(CH 3CN)H (Tp = hydrotris(pyrazolyl)borate) catalyzes H/D exchange between CH 4 and some deuterated organic solvents-benzene-d 6, tetrahydrofuran-d 8, diethyl ether-d 10, and dioxane-d 8. Preferential cleavage of the α-C-D and the β-C-D bonds of THF-d 8 and diethyl ether-d 10, respectively, is observed. The H/D exchange processes have been investigated by density functional theory calculations at the B3LYP level. Theoretical study on the reaction mechanism suggests that σ-complexes TpRu(PPh 3)(η 2-H-R)H are active species in the exchange processes. During the exchange processes, the reversible transformations of TpRu(PPh 3)(η 2-H-R)H to TpRu(PPh 3)(η 2-H 2)R are the crucial steps. The barriers for the transformations are in the range 10-13.4 kcal/mol. Interestingly, the transition states for the transformations correspond to the seven-coordinate TpRu(PPh 3)(R)(H)(H), which are species derived from the oxidative addition of H-R to the metal center. The exchange processes involve transformations of the (η 2-H-R) species to the (η 2-H 2) species followed by H-H rotation in the latter. The rotation barriers are calculated to be in the range 2-4 kcal/mol. The exchange process having an aromatic R group is found to be most favorable due to the strong Ru-C(sp 2) bonding, which stabilizes the (η 2-H 2) species and lowers the transformation barrier. The complex TpRu(PPh 3)(CH 3CN)H catalyzes H/D exchange between H 2 and the deuterated solvents too.en_US
dc.languageengen_US
dc.publisherAmerican Chemical Society. The Journal's web site is located at http://pubs.acs.org/organometallicsen_US
dc.relation.ispartofOrganometallicsen_US
dc.titleC-H bond activation by a hydrotris(pyrazolyl)borato ruthenium hydride complexen_US
dc.typeArticleen_US
dc.identifier.emailLam, WH:chsue@hku.hken_US
dc.identifier.authorityLam, WH=rp00719en_US
dc.description.naturelink_to_subscribed_fulltexten_US
dc.identifier.doi10.1021/om0209024en_US
dc.identifier.scopuseid_2-s2.0-0037450851en_US
dc.relation.referenceshttp://www.scopus.com/mlt/select.url?eid=2-s2.0-0037450851&selection=ref&src=s&origin=recordpageen_US
dc.identifier.volume22en_US
dc.identifier.issue4en_US
dc.identifier.spage641en_US
dc.identifier.epage651en_US
dc.identifier.isiWOS:000181024000009-
dc.publisher.placeUnited Statesen_US
dc.identifier.scopusauthoridNg, SM=37004088600en_US
dc.identifier.scopusauthoridLam, WH=26642862800en_US
dc.identifier.scopusauthoridMak, CC=7102876301en_US
dc.identifier.scopusauthoridTsang, CW=7202935952en_US
dc.identifier.scopusauthoridJia, G=7103360705en_US
dc.identifier.scopusauthoridLin, Z=7404230177en_US
dc.identifier.scopusauthoridLau, CP=7401968356en_US

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