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Article: Syntheses, spectroscopy, and electrochemistry of high-valent osmium(V) and -(VI) oxo complexes of macrocyclic tertiary amine ligands
Title | Syntheses, spectroscopy, and electrochemistry of high-valent osmium(V) and -(VI) oxo complexes of macrocyclic tertiary amine ligands |
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Authors | |
Issue Date | 1990 |
Publisher | Royal 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? |
Abstract | Osmium 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 Identifier | http://hdl.handle.net/10722/168158 |
ISSN | |
ISI Accession Number ID |
DC Field | Value | Language |
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dc.contributor.author | Che, CM | en_US |
dc.contributor.author | Cheng, WK | en_US |
dc.contributor.author | Yam, VWW | en_US |
dc.date.accessioned | 2012-10-08T03:15:46Z | - |
dc.date.available | 2012-10-08T03:15:46Z | - |
dc.date.issued | 1990 | en_US |
dc.identifier.citation | Journal Of The Chemical Society, Dalton Transactions, 1990 n. 10, p. 3095-3100 | en_US |
dc.identifier.issn | 1472-7773 | en_US |
dc.identifier.uri | http://hdl.handle.net/10722/168158 | - |
dc.description.abstract | Osmium 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.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 | Journal of the Chemical Society, Dalton Transactions | en_US |
dc.title | Syntheses, spectroscopy, and electrochemistry of high-valent osmium(V) and -(VI) oxo complexes of macrocyclic tertiary amine ligands | en_US |
dc.type | Article | en_US |
dc.identifier.email | Che, CM:cmche@hku.hk | en_US |
dc.identifier.email | Yam, VWW:wwyam@hku.hk | en_US |
dc.identifier.authority | Che, CM=rp00670 | en_US |
dc.identifier.authority | Yam, VWW=rp00822 | en_US |
dc.description.nature | link_to_subscribed_fulltext | en_US |
dc.identifier.doi | 10.1039/DT9900003095 | en_US |
dc.identifier.scopus | eid_2-s2.0-37049066391 | en_US |
dc.identifier.issue | 10 | en_US |
dc.identifier.spage | 3095 | en_US |
dc.identifier.epage | 3100 | en_US |
dc.identifier.isi | WOS:A1990ED73300025 | - |
dc.publisher.place | United Kingdom | en_US |
dc.identifier.scopusauthorid | Che, CM=7102442791 | en_US |
dc.identifier.scopusauthorid | Cheng, WK=7402169559 | en_US |
dc.identifier.scopusauthorid | Yam, VWW=18539304700 | en_US |
dc.identifier.issnl | 1364-5447 | - |