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Article: Photoredox properties of [osN(NH3)4]3+ and mechanism of formation of [{Os(NH3)4(CH3CN)}2N 2]5+ through a nitrido-coupling reaction

TitlePhotoredox properties of [osN(NH3)4]3+ and mechanism of formation of [{Os(NH3)4(CH3CN)}2N 2]5+ through a nitrido-coupling reaction
Authors
Issue Date1992
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, 1992 n. 8, p. 1411-1416 How to Cite?
AbstractThe oxidation of [Os(NH3)5Cl]2+ by CeIV in water gave [OsN(NH3)4]3+ quantitatively. Excitation of [OsN(NH3)4]3+ in the solid state or in solution at 300-400 nm resulted in room-temperature photoluminescence. The low-lying spin orbital E sublevel of the 3E {3[(dxy)1(dπ*) 1]} state was assigned as the emission state. The excited state of [OsN(NH3)4]3+ was quenched by electron donors such as aromatic hydrocarbons, alkoxybenzenes, amines and alcohols. A photoinduced electron-transfer mechanism is proposed for the quenching processes. The emission lifetime of [OsN(NH3)4]3+ depended on the complex concentration. An excited-state bimolecular self-quenching mechanism ([OsVI≡N]* + [OsVI≡N] → product) is likely. Photolysis of [OsN(NH3)4]3+ in the presence of an electron donor such as 1,4-dimethoxybenzene or C6Me6 in acetonitrile led to the formation of the μ-dinitrogen product [{Os(NH3)4(CH3CN)}2N 2]5+. The coupling reaction obeyed the kinetics rate = k2[OsVI][OsV] where k2 was estimated to be (3.75 ± 0.30) × 105 dm3 mol-1 s-1 at 298 K. Oxidation of [{Os(NH3)4 -(CH3CN)} 2N2]5+ by CeIV in water followed by precipitation with 2 mol dm-3 HCl gave the product [OsN(NH3)4]Cl3 in detectable yield.
Persistent Identifierhttp://hdl.handle.net/10722/168237
ISSN
2002 Impact Factor: 3.023
ISI Accession Number ID

 

DC FieldValueLanguage
dc.contributor.authorLam, HWen_US
dc.contributor.authorChe, CMen_US
dc.contributor.authorWong, KYen_US
dc.date.accessioned2012-10-08T03:16:33Z-
dc.date.available2012-10-08T03:16:33Z-
dc.date.issued1992en_US
dc.identifier.citationJournal Of The Chemical Society, Dalton Transactions, 1992 n. 8, p. 1411-1416en_US
dc.identifier.issn1472-7773en_US
dc.identifier.urihttp://hdl.handle.net/10722/168237-
dc.description.abstractThe oxidation of [Os(NH3)5Cl]2+ by CeIV in water gave [OsN(NH3)4]3+ quantitatively. Excitation of [OsN(NH3)4]3+ in the solid state or in solution at 300-400 nm resulted in room-temperature photoluminescence. The low-lying spin orbital E sublevel of the 3E {3[(dxy)1(dπ*) 1]} state was assigned as the emission state. The excited state of [OsN(NH3)4]3+ was quenched by electron donors such as aromatic hydrocarbons, alkoxybenzenes, amines and alcohols. A photoinduced electron-transfer mechanism is proposed for the quenching processes. The emission lifetime of [OsN(NH3)4]3+ depended on the complex concentration. An excited-state bimolecular self-quenching mechanism ([OsVI≡N]* + [OsVI≡N] → product) is likely. Photolysis of [OsN(NH3)4]3+ in the presence of an electron donor such as 1,4-dimethoxybenzene or C6Me6 in acetonitrile led to the formation of the μ-dinitrogen product [{Os(NH3)4(CH3CN)}2N 2]5+. The coupling reaction obeyed the kinetics rate = k2[OsVI][OsV] where k2 was estimated to be (3.75 ± 0.30) × 105 dm3 mol-1 s-1 at 298 K. Oxidation of [{Os(NH3)4 -(CH3CN)} 2N2]5+ by CeIV in water followed by precipitation with 2 mol dm-3 HCl gave the product [OsN(NH3)4]Cl3 in detectable yield.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.titlePhotoredox properties of [osN(NH3)4]3+ and mechanism of formation of [{Os(NH3)4(CH3CN)}2N 2]5+ through a nitrido-coupling reactionen_US
dc.typeArticleen_US
dc.identifier.emailChe, CM:cmche@hku.hken_US
dc.identifier.authorityChe, CM=rp00670en_US
dc.description.naturelink_to_subscribed_fulltexten_US
dc.identifier.doi10.1039/DT9920001411en_US
dc.identifier.scopuseid_2-s2.0-37049086654en_US
dc.identifier.issue8en_US
dc.identifier.spage1411en_US
dc.identifier.epage1416en_US
dc.identifier.isiWOS:A1992HQ62000013-
dc.publisher.placeUnited Kingdomen_US
dc.identifier.scopusauthoridLam, HW=23067533600en_US
dc.identifier.scopusauthoridChe, CM=7102442791en_US
dc.identifier.scopusauthoridWong, KY=7404760030en_US

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