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Article: Syntheses, spectroscopy, and electrochemistry of high-valent osmium(V) and -(VI) oxo complexes of macrocyclic tertiary amine ligands

TitleSyntheses, spectroscopy, and electrochemistry of high-valent osmium(V) and -(VI) oxo complexes of macrocyclic tertiary amine ligands
Authors
Issue Date1990
PublisherRoyal Society of Chemistry. The Journal's web site is located at http://www.rsc.org/dalton
Citation
Journal Of The Chemical Society, Dalton Transactions, 1990 n. 10, p. 3095-3100 How to Cite?
AbstractOsmium has been inserted into macrocyclic tertiary amine ligands [L = 1,4,8,11-tetramethyl-1,4,8,11-tetra-azacyclotetradecane, 1,4,8,12-tetramethyl-1,4,8,12-tetra-azacyclopentadecane, 1,5,9,13-tetramethyl-1,5,9,13-tetra-azacyclohexadecane, and meso-2,3,7,11,12-pentamethyl-3,7,11,17-tetra-azabicyclo[11.3.1]heptadeca-1(17), 13,15-triene] to give trans-[OsIIILCl2]+, which could be oxidized to trans-[OsVIL(O)2]2+ by H2O2. The trans-[OsVIL(O)2]2+ complexes show one intense νasym(OsO2) stretch at 870-880 cm-1. Their u.v.-visible spectra display two vibronic structured electronic absorption bands centred at ca. 310 and 350 nm, assignable to the spin-allowed and spin-forbidden (dxy)2 → (dxy)1(dπ*)1 transitions (dπ* = dxz′dyz). Room-temperature photoluminescence with emission maxima in the region 620-710 nm from trans-[OsVIL(O) 2]2+ has been observed. In acetonitrile, trans-[OsVIL(O)2]2+ displays reversible OsVI-OsV and Os V-OsIV couples with E⊖ ranging from -0.67 to -0.73 and -1.48 to -1.74 V vs. ferrocenium-ferrocene, respectively. The complexes trans-[ OsVL(O)2]+ have been characterized by u.v.-visible spectroscopy and magnetic susceptibility measurements. In aqueous solutions, pH-dependent and reversible OsVI-OsIII couples have been observed. Thermally, trans-[OsVIL(O)2]2+ complexes are poor oxidants for alkene oxidation.
Persistent Identifierhttp://hdl.handle.net/10722/168158
ISSN
2002 Impact Factor: 3.023
ISI Accession Number ID

 

DC FieldValueLanguage
dc.contributor.authorChe, CMen_US
dc.contributor.authorCheng, WKen_US
dc.contributor.authorYam, VWWen_US
dc.date.accessioned2012-10-08T03:15:46Z-
dc.date.available2012-10-08T03:15:46Z-
dc.date.issued1990en_US
dc.identifier.citationJournal Of The Chemical Society, Dalton Transactions, 1990 n. 10, p. 3095-3100en_US
dc.identifier.issn1472-7773en_US
dc.identifier.urihttp://hdl.handle.net/10722/168158-
dc.description.abstractOsmium has been inserted into macrocyclic tertiary amine ligands [L = 1,4,8,11-tetramethyl-1,4,8,11-tetra-azacyclotetradecane, 1,4,8,12-tetramethyl-1,4,8,12-tetra-azacyclopentadecane, 1,5,9,13-tetramethyl-1,5,9,13-tetra-azacyclohexadecane, and meso-2,3,7,11,12-pentamethyl-3,7,11,17-tetra-azabicyclo[11.3.1]heptadeca-1(17), 13,15-triene] to give trans-[OsIIILCl2]+, which could be oxidized to trans-[OsVIL(O)2]2+ by H2O2. The trans-[OsVIL(O)2]2+ complexes show one intense νasym(OsO2) stretch at 870-880 cm-1. Their u.v.-visible spectra display two vibronic structured electronic absorption bands centred at ca. 310 and 350 nm, assignable to the spin-allowed and spin-forbidden (dxy)2 → (dxy)1(dπ*)1 transitions (dπ* = dxz′dyz). Room-temperature photoluminescence with emission maxima in the region 620-710 nm from trans-[OsVIL(O) 2]2+ has been observed. In acetonitrile, trans-[OsVIL(O)2]2+ displays reversible OsVI-OsV and Os V-OsIV couples with E⊖ ranging from -0.67 to -0.73 and -1.48 to -1.74 V vs. ferrocenium-ferrocene, respectively. The complexes trans-[ OsVL(O)2]+ have been characterized by u.v.-visible spectroscopy and magnetic susceptibility measurements. In aqueous solutions, pH-dependent and reversible OsVI-OsIII couples have been observed. Thermally, trans-[OsVIL(O)2]2+ complexes are poor oxidants for alkene oxidation.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.ispartofJournal of the Chemical Society, Dalton Transactionsen_US
dc.titleSyntheses, spectroscopy, and electrochemistry of high-valent osmium(V) and -(VI) oxo complexes of macrocyclic tertiary amine ligandsen_US
dc.typeArticleen_US
dc.identifier.emailChe, CM:cmche@hku.hken_US
dc.identifier.emailYam, VWW:wwyam@hku.hken_US
dc.identifier.authorityChe, CM=rp00670en_US
dc.identifier.authorityYam, VWW=rp00822en_US
dc.description.naturelink_to_subscribed_fulltexten_US
dc.identifier.doi10.1039/DT9900003095en_US
dc.identifier.scopuseid_2-s2.0-37049066391en_US
dc.identifier.issue10en_US
dc.identifier.spage3095en_US
dc.identifier.epage3100en_US
dc.identifier.isiWOS:A1990ED73300025-
dc.publisher.placeUnited Kingdomen_US
dc.identifier.scopusauthoridChe, CM=7102442791en_US
dc.identifier.scopusauthoridCheng, WK=7402169559en_US
dc.identifier.scopusauthoridYam, VWW=18539304700en_US

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