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- Publisher Website: 10.1039/B402632B
- Scopus: eid_2-s2.0-3042765623
- PMID: 15252604
- WOS: WOS:000221287800011
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Article: Theoretical study of reaction pathways for the rhodium phosphinecatalysed borylation of C-H bonds with pinacolborane
Title | Theoretical study of reaction pathways for the rhodium phosphinecatalysed borylation of C-H bonds with pinacolborane |
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Authors | |
Issue Date | 2004 |
Publisher | Royal Society of Chemistry. The Journal's web site is located at http://www.rsc.org/dalton |
Citation | Dalton Transactions, 2004 n. 10, p. 1556-1562 How to Cite? |
Abstract | The reaction mechanism of the rhodium-phosphine catalysed borylation of methyl-substituted arenes using pinacolborane (HBpin) has been investigated theoretically using DFT calculations at the B3PW91 level. Factors affecting selectivity for benzylic vs. aromatic C-H bond activation have been examined. It was found that [Rh(PR3)2(H)] is the active species which oxidatively adds the C-H bond leading to an η3-benzyl complex which is the key to determining the unusual benzylic regioselectivity observed experimentally for this catalyst system. Subsequent reaction with HBpin leads to a [Rh(PR3)2(η3-benzyl)(H)(Bpin)] complex from which B-C reductive elimination provides product and regenerates the catalyst. The electrophilic nature of the boryl ligand assists in the reductive elimination process. In contrast to Ir(L)2(boryl)3-based catalysts, for which Ir(III)-Ir(v) cycles have been proposed, the Rh(I)-Rh(III) cycle is operating with the system addressed herein. |
Persistent Identifier | http://hdl.handle.net/10722/167989 |
ISSN | 2023 Impact Factor: 3.5 2023 SCImago Journal Rankings: 0.697 |
ISI Accession Number ID | |
References |
DC Field | Value | Language |
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dc.contributor.author | Lam, WH | en_US |
dc.contributor.author | Lam, KC | en_US |
dc.contributor.author | Lin, Z | en_US |
dc.contributor.author | Shimada, S | en_US |
dc.contributor.author | Perutz, RN | en_US |
dc.contributor.author | Marder, TB | en_US |
dc.date.accessioned | 2012-10-08T03:13:47Z | - |
dc.date.available | 2012-10-08T03:13:47Z | - |
dc.date.issued | 2004 | en_US |
dc.identifier.citation | Dalton Transactions, 2004 n. 10, p. 1556-1562 | en_US |
dc.identifier.issn | 1477-9226 | en_US |
dc.identifier.uri | http://hdl.handle.net/10722/167989 | - |
dc.description.abstract | The reaction mechanism of the rhodium-phosphine catalysed borylation of methyl-substituted arenes using pinacolborane (HBpin) has been investigated theoretically using DFT calculations at the B3PW91 level. Factors affecting selectivity for benzylic vs. aromatic C-H bond activation have been examined. It was found that [Rh(PR3)2(H)] is the active species which oxidatively adds the C-H bond leading to an η3-benzyl complex which is the key to determining the unusual benzylic regioselectivity observed experimentally for this catalyst system. Subsequent reaction with HBpin leads to a [Rh(PR3)2(η3-benzyl)(H)(Bpin)] complex from which B-C reductive elimination provides product and regenerates the catalyst. The electrophilic nature of the boryl ligand assists in the reductive elimination process. In contrast to Ir(L)2(boryl)3-based catalysts, for which Ir(III)-Ir(v) cycles have been proposed, the Rh(I)-Rh(III) cycle is operating with the system addressed herein. | en_US |
dc.language | eng | en_US |
dc.publisher | Royal Society of Chemistry. The Journal's web site is located at http://www.rsc.org/dalton | en_US |
dc.relation.ispartof | Dalton Transactions | en_US |
dc.title | Theoretical study of reaction pathways for the rhodium phosphinecatalysed borylation of C-H bonds with pinacolborane | 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 | 10.1039/B402632B | - |
dc.identifier.pmid | 15252604 | - |
dc.identifier.scopus | eid_2-s2.0-3042765623 | en_US |
dc.relation.references | http://www.scopus.com/mlt/select.url?eid=2-s2.0-3042765623&selection=ref&src=s&origin=recordpage | en_US |
dc.identifier.issue | 10 | en_US |
dc.identifier.spage | 1556 | en_US |
dc.identifier.epage | 1562 | en_US |
dc.identifier.isi | WOS:000221287800011 | - |
dc.publisher.place | United Kingdom | en_US |
dc.identifier.scopusauthorid | Lam, WH=26642862800 | en_US |
dc.identifier.scopusauthorid | Lam, KC=8207496000 | en_US |
dc.identifier.scopusauthorid | Lin, Z=7404230177 | en_US |
dc.identifier.scopusauthorid | Shimada, S=7402762440 | en_US |
dc.identifier.scopusauthorid | Perutz, RN=7006907321 | en_US |
dc.identifier.scopusauthorid | Marder, TB=7006433068 | en_US |
dc.identifier.issnl | 1477-9226 | - |