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Article: Theoretical study of reaction pathways for the rhodium phosphinecatalysed borylation of C-H bonds with pinacolborane

TitleTheoretical study of reaction pathways for the rhodium phosphinecatalysed borylation of C-H bonds with pinacolborane
Authors
Issue Date2004
PublisherRoyal 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?
AbstractThe 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 Identifierhttp://hdl.handle.net/10722/167989
ISSN
2015 Impact Factor: 4.177
2015 SCImago Journal Rankings: 1.404
ISI Accession Number ID
References

 

DC FieldValueLanguage
dc.contributor.authorLam, WHen_US
dc.contributor.authorLam, KCen_US
dc.contributor.authorLin, Zen_US
dc.contributor.authorShimada, Sen_US
dc.contributor.authorPerutz, RNen_US
dc.contributor.authorMarder, TBen_US
dc.date.accessioned2012-10-08T03:13:47Z-
dc.date.available2012-10-08T03:13:47Z-
dc.date.issued2004en_US
dc.identifier.citationDalton Transactions, 2004 n. 10, p. 1556-1562en_US
dc.identifier.issn1477-9226en_US
dc.identifier.urihttp://hdl.handle.net/10722/167989-
dc.description.abstractThe 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.languageengen_US
dc.publisherRoyal Society of Chemistry. The Journal's web site is located at http://www.rsc.org/daltonen_US
dc.relation.ispartofDalton Transactionsen_US
dc.titleTheoretical study of reaction pathways for the rhodium phosphinecatalysed borylation of C-H bonds with pinacolboraneen_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.doi10.1039/B402632B-
dc.identifier.pmid15252604-
dc.identifier.scopuseid_2-s2.0-3042765623en_US
dc.relation.referenceshttp://www.scopus.com/mlt/select.url?eid=2-s2.0-3042765623&selection=ref&src=s&origin=recordpageen_US
dc.identifier.issue10en_US
dc.identifier.spage1556en_US
dc.identifier.epage1562en_US
dc.identifier.isiWOS:000221287800011-
dc.publisher.placeUnited Kingdomen_US
dc.identifier.scopusauthoridLam, WH=26642862800en_US
dc.identifier.scopusauthoridLam, KC=8207496000en_US
dc.identifier.scopusauthoridLin, Z=7404230177en_US
dc.identifier.scopusauthoridShimada, S=7402762440en_US
dc.identifier.scopusauthoridPerutz, RN=7006907321en_US
dc.identifier.scopusauthoridMarder, TB=7006433068en_US

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