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Article: C-H bond activation by a hydrotris(pyrazolyl)borato ruthenium hydride complex
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TitleC-H bond activation by a hydrotris(pyrazolyl)borato ruthenium hydride complex
 
AuthorsNg, SM1
Lam, WH2
Mak, CC1
Tsang, CW1
Jia, G2
Lin, Z2
Lau, CP1
 
Issue Date2003
 
PublisherAmerican Chemical Society. The Journal's web site is located at http://pubs.acs.org/organometallics
 
CitationOrganometallics, 2003, v. 22 n. 4, p. 641-651 [How to Cite?]
DOI: http://dx.doi.org/10.1021/om0209024
 
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.
 
ISSN0276-7333
2013 Impact Factor: 4.253
 
DOIhttp://dx.doi.org/10.1021/om0209024
 
ISI Accession Number IDWOS:000181024000009
 
ReferencesReferences in Scopus
 
DC FieldValue
dc.contributor.authorNg, SM
 
dc.contributor.authorLam, WH
 
dc.contributor.authorMak, CC
 
dc.contributor.authorTsang, CW
 
dc.contributor.authorJia, G
 
dc.contributor.authorLin, Z
 
dc.contributor.authorLau, CP
 
dc.date.accessioned2012-10-08T03:11:35Z
 
dc.date.available2012-10-08T03:11:35Z
 
dc.date.issued2003
 
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.
 
dc.description.naturelink_to_subscribed_fulltext
 
dc.identifier.citationOrganometallics, 2003, v. 22 n. 4, p. 641-651 [How to Cite?]
DOI: http://dx.doi.org/10.1021/om0209024
 
dc.identifier.doihttp://dx.doi.org/10.1021/om0209024
 
dc.identifier.epage651
 
dc.identifier.isiWOS:000181024000009
 
dc.identifier.issn0276-7333
2013 Impact Factor: 4.253
 
dc.identifier.issue4
 
dc.identifier.scopuseid_2-s2.0-0037450851
 
dc.identifier.spage641
 
dc.identifier.urihttp://hdl.handle.net/10722/167786
 
dc.identifier.volume22
 
dc.languageeng
 
dc.publisherAmerican Chemical Society. The Journal's web site is located at http://pubs.acs.org/organometallics
 
dc.publisher.placeUnited States
 
dc.relation.ispartofOrganometallics
 
dc.relation.referencesReferences in Scopus
 
dc.titleC-H bond activation by a hydrotris(pyrazolyl)borato ruthenium hydride complex
 
dc.typeArticle
 
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<description.abstract>The 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 &#945;-C-D and the &#946;-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 &#963;-complexes TpRu(PPh 3)(&#951; 2-H-R)H are active species in the exchange processes. During the exchange processes, the reversible transformations of TpRu(PPh 3)(&#951; 2-H-R)H to TpRu(PPh 3)(&#951; 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 (&#951; 2-H-R) species to the (&#951; 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 (&#951; 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.</description.abstract>
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Author Affiliations
  1. Hong Kong Polytechnic University
  2. Hong Kong University of Science and Technology