File Download

There are no files associated with this item.

  Links for fulltext
     (May Require Subscription)
Supplementary

Article: Ruthenium and osmium porphyrin carbene complexes: Synthesis, structure, and connection to the metal-mediated cyclopropanation of alkenes

TitleRuthenium and osmium porphyrin carbene complexes: Synthesis, structure, and connection to the metal-mediated cyclopropanation of alkenes
Authors
KeywordsMetal-carbene complexes
Metal-catalyzed cyclopropanations
Ruthenium and osmium porphyrins
Issue Date2002
PublisherElsevier BV. The Journal's web site is located at http://www.elsevier.com/locate/ccr
Citation
Coordination Chemistry Reviews, 2002, v. 231 n. 1-2, p. 151-164 How to Cite?
AbstractA series of monocarbene ruthenium/osmium porphyrins [M(Por)(CRR′)] (M = Ru, Os; R=R′ in some cases) and two biscarbene osmium porphyrins [Os(Por)(CR2)2] have been prepared by several research groups from reactions of diazo compounds with ruthenium/osmium porphyrins [M(Por)]2, [M(Por)(CO)] (M = Ru, Os), [Ru(Por)], or [Os(Por)(CR2)], or from reactions of K2[Ru(Por)] with germinal dihalides. The structures of [Os(TTP)(CRR′)(THF)] (CRR′=C(p-C6H4CH3)2, CHSiMe3), [Ru(TPP)(C(CO2Et)2)(MeOH)], [Ru(Por*)(CRR′)] (CRR′=CPh2, C(Ph)CO2CH2CH=CH2), [Os(TPFPP)(CPh2)(MeOH)], and [Os(TPFPP)(CPh2)2] have been determined by X-ray crystallography, which feature M=C(carbene) bond lengths of 1.79(2)-1.870(2) Å for the monocarbene complexes and 2.035(2), 2.027(3) Å for the biscarbene complex. Reactions of [Os(TTP)(CHR)] (R = C02Et, SiMe3) with para-substituted pyridines 4-X-C5H4N afford osmium porphyrin ylide complexes [Os(TTP)(CH(R)(4-X-C5H4N)) (4-X-C5H4N)]. The complexes [Os(TTP)(CHCO2Et)], [Ru(TPP)(C(CO2Et)2)], and [Os(TPFPP)(CPh2)2] all undergo cyclopropanation reactions with styrene. The biscarbene complex [Os(TPFPP)(CPh2)2] also reacts with unfunctionalized alkenes such as cyclohexene to yield C-H insertion products. A few ruthenium/osmium porphyrin carbene complexes, including [Os(TTP)(CHCO2Et)], [Ru(TPP)(CHCO2Et)], [Ru(Por*)(CHX)(L)] (X = CO2R, CO2CH2CH=CRCRt; L = a ligand with considerable trans effect such as CHX), and [Os(TPFPP)(CPh2)2], are proposed to be the active intermediates in the corresponding ruthenium/osmium porphyrin-catalyzed alkene cyclopropanations. © 2002 Elsevier Science B.V. All rights reserved.
Persistent Identifierhttp://hdl.handle.net/10722/70001
ISSN
2015 Impact Factor: 12.994
2015 SCImago Journal Rankings: 4.100
ISI Accession Number ID
References

 

DC FieldValueLanguage
dc.contributor.authorChe, CMen_HK
dc.contributor.authorHuang, JSen_HK
dc.date.accessioned2010-09-06T06:18:47Z-
dc.date.available2010-09-06T06:18:47Z-
dc.date.issued2002en_HK
dc.identifier.citationCoordination Chemistry Reviews, 2002, v. 231 n. 1-2, p. 151-164en_HK
dc.identifier.issn0010-8545en_HK
dc.identifier.urihttp://hdl.handle.net/10722/70001-
dc.description.abstractA series of monocarbene ruthenium/osmium porphyrins [M(Por)(CRR′)] (M = Ru, Os; R=R′ in some cases) and two biscarbene osmium porphyrins [Os(Por)(CR2)2] have been prepared by several research groups from reactions of diazo compounds with ruthenium/osmium porphyrins [M(Por)]2, [M(Por)(CO)] (M = Ru, Os), [Ru(Por)], or [Os(Por)(CR2)], or from reactions of K2[Ru(Por)] with germinal dihalides. The structures of [Os(TTP)(CRR′)(THF)] (CRR′=C(p-C6H4CH3)2, CHSiMe3), [Ru(TPP)(C(CO2Et)2)(MeOH)], [Ru(Por*)(CRR′)] (CRR′=CPh2, C(Ph)CO2CH2CH=CH2), [Os(TPFPP)(CPh2)(MeOH)], and [Os(TPFPP)(CPh2)2] have been determined by X-ray crystallography, which feature M=C(carbene) bond lengths of 1.79(2)-1.870(2) Å for the monocarbene complexes and 2.035(2), 2.027(3) Å for the biscarbene complex. Reactions of [Os(TTP)(CHR)] (R = C02Et, SiMe3) with para-substituted pyridines 4-X-C5H4N afford osmium porphyrin ylide complexes [Os(TTP)(CH(R)(4-X-C5H4N)) (4-X-C5H4N)]. The complexes [Os(TTP)(CHCO2Et)], [Ru(TPP)(C(CO2Et)2)], and [Os(TPFPP)(CPh2)2] all undergo cyclopropanation reactions with styrene. The biscarbene complex [Os(TPFPP)(CPh2)2] also reacts with unfunctionalized alkenes such as cyclohexene to yield C-H insertion products. A few ruthenium/osmium porphyrin carbene complexes, including [Os(TTP)(CHCO2Et)], [Ru(TPP)(CHCO2Et)], [Ru(Por*)(CHX)(L)] (X = CO2R, CO2CH2CH=CRCRt; L = a ligand with considerable trans effect such as CHX), and [Os(TPFPP)(CPh2)2], are proposed to be the active intermediates in the corresponding ruthenium/osmium porphyrin-catalyzed alkene cyclopropanations. © 2002 Elsevier Science B.V. All rights reserved.en_HK
dc.languageengen_HK
dc.publisherElsevier BV. The Journal's web site is located at http://www.elsevier.com/locate/ccren_HK
dc.relation.ispartofCoordination Chemistry Reviewsen_HK
dc.rightsCoordination Chemistry Reviews. Copyright © Elsevier BV.en_HK
dc.subjectMetal-carbene complexesen_HK
dc.subjectMetal-catalyzed cyclopropanationsen_HK
dc.subjectRuthenium and osmium porphyrinsen_HK
dc.titleRuthenium and osmium porphyrin carbene complexes: Synthesis, structure, and connection to the metal-mediated cyclopropanation of alkenesen_HK
dc.typeArticleen_HK
dc.identifier.openurlhttp://library.hku.hk:4550/resserv?sid=HKU:IR&issn=0010-8545&volume=231&spage=151&epage=164&date=2002&atitle=Ruthenium+and+osmium+porphyrin+carbene+complexes:++synthesis,+structure,+and+connection+to+the+metal-mediated+cyclopropanation+of+alkenesen_HK
dc.identifier.emailChe, CM:cmche@hku.hken_HK
dc.identifier.emailHuang, JS:jshuang@hkucc.hku.hken_HK
dc.identifier.authorityChe, CM=rp00670en_HK
dc.identifier.authorityHuang, JS=rp00709en_HK
dc.description.naturelink_to_subscribed_fulltext-
dc.identifier.doi10.1016/S0010-8545(02)00117-0en_HK
dc.identifier.scopuseid_2-s2.0-0036731525en_HK
dc.identifier.hkuros76366en_HK
dc.relation.referenceshttp://www.scopus.com/mlt/select.url?eid=2-s2.0-0036731525&selection=ref&src=s&origin=recordpageen_HK
dc.identifier.volume231en_HK
dc.identifier.issue1-2en_HK
dc.identifier.spage151en_HK
dc.identifier.epage164en_HK
dc.identifier.isiWOS:000178013500007-
dc.publisher.placeNetherlandsen_HK
dc.identifier.scopusauthoridChe, CM=7102442791en_HK
dc.identifier.scopusauthoridHuang, JS=7407192639en_HK

Export via OAI-PMH Interface in XML Formats


OR


Export to Other Non-XML Formats