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Article: C-H bond activation by a hydrotris(pyrazolyl)borato ruthenium hydride complex
Title | C-H bond activation by a hydrotris(pyrazolyl)borato ruthenium hydride complex |
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Authors | |
Issue Date | 2003 |
Publisher | American 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? |
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 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 Identifier | http://hdl.handle.net/10722/167786 |
ISSN | 2023 Impact Factor: 2.5 2023 SCImago Journal Rankings: 0.654 |
ISI Accession Number ID | |
References |
DC Field | Value | Language |
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dc.contributor.author | Ng, SM | en_US |
dc.contributor.author | Lam, WH | en_US |
dc.contributor.author | Mak, CC | en_US |
dc.contributor.author | Tsang, CW | en_US |
dc.contributor.author | Jia, G | en_US |
dc.contributor.author | Lin, Z | en_US |
dc.contributor.author | Lau, CP | en_US |
dc.date.accessioned | 2012-10-08T03:11:35Z | - |
dc.date.available | 2012-10-08T03:11:35Z | - |
dc.date.issued | 2003 | en_US |
dc.identifier.citation | Organometallics, 2003, v. 22 n. 4, p. 641-651 | en_US |
dc.identifier.issn | 0276-7333 | en_US |
dc.identifier.uri | http://hdl.handle.net/10722/167786 | - |
dc.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 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.language | eng | en_US |
dc.publisher | American Chemical Society. The Journal's web site is located at http://pubs.acs.org/organometallics | en_US |
dc.relation.ispartof | Organometallics | en_US |
dc.title | C-H bond activation by a hydrotris(pyrazolyl)borato ruthenium hydride complex | en_US |
dc.type | Article | en_US |
dc.identifier.email | Lam, WH:chsue@hku.hk | en_US |
dc.identifier.authority | Lam, WH=rp00719 | en_US |
dc.description.nature | link_to_subscribed_fulltext | en_US |
dc.identifier.doi | 10.1021/om0209024 | en_US |
dc.identifier.scopus | eid_2-s2.0-0037450851 | en_US |
dc.relation.references | http://www.scopus.com/mlt/select.url?eid=2-s2.0-0037450851&selection=ref&src=s&origin=recordpage | en_US |
dc.identifier.volume | 22 | en_US |
dc.identifier.issue | 4 | en_US |
dc.identifier.spage | 641 | en_US |
dc.identifier.epage | 651 | en_US |
dc.identifier.isi | WOS:000181024000009 | - |
dc.publisher.place | United States | en_US |
dc.identifier.scopusauthorid | Ng, SM=37004088600 | en_US |
dc.identifier.scopusauthorid | Lam, WH=26642862800 | en_US |
dc.identifier.scopusauthorid | Mak, CC=7102876301 | en_US |
dc.identifier.scopusauthorid | Tsang, CW=7202935952 | en_US |
dc.identifier.scopusauthorid | Jia, G=7103360705 | en_US |
dc.identifier.scopusauthorid | Lin, Z=7404230177 | en_US |
dc.identifier.scopusauthorid | Lau, CP=7401968356 | en_US |
dc.identifier.issnl | 0276-7333 | - |