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Article: Structural and mechanistic studies of coordination compounds. 36. Electronic spectra and photochemistry of some trans-(tetraamine)ruthenium(III) complexes

TitleStructural and mechanistic studies of coordination compounds. 36. Electronic spectra and photochemistry of some trans-(tetraamine)ruthenium(III) complexes
Authors
Issue Date1983
PublisherAmerican Chemical Society. The Journal's web site is located at http://pubs.acs.org/ic
Citation
Inorganic Chemistry, 1983, v. 22 n. 26, p. 3893-3898 How to Cite?
AbstractThe electronic absorption spectra of an extensive series of tetraamine complexes of the type trans-[RuLX2]+ (X = Cl, Br, or I) have been analyzed. In general, two ligand-to-metal charge-transfer (CTTM) transitions of (pπ)x → dπ* origin are observed. The wavelength of the lowest energy band increases gradually with increasing chelation and steric congestion of the amine ligand L around the ruthenium(III) ion. The splitting of the (pπ)x → dπ* transition is largest for the two sterically congested teta and tetb complexes, where teta and tetb represent C-meso- and C-rac-5,5,7,12,12,14-hexa-methyl-1,4,8,11-tetraazacyclotetradecane, respectively, but decreases with the nature of X, Cl > Br > I. The spectra of trans-[Ru(cyclam)X2]X (X = Cl or Br) have been resolved at low temperature (∼30 K), and (pσ)x → dπ* transitions have been assigned to some of these resolved bands. Photochemistry of trans-[RuLIX]+ (L = (en)2, X = Cl, Br, or I; L = 2,3,2-tet or cyclam, X = I; en, 2,3,2-tet, and cyclam represent ethane-1,2-diamine, 3,7-diazanonane-1,9-diamine, and 1,4,8,11-tetraazacyclotetradecane, respectively) has been investigated. Irradiation at the lowest CTTM band (λirr > 500 nm) leads to stereoretentive aquation of X- with quantum yields independent of X but decreasing with increasing chelation of L. Domination of the RuII-I• entity in the CTTM excited state has been discussed. Irradiation of the second CTTM band leads to photoaquation with concomitant stereochemical change. The results are interpreted in terms of a quartet ligand field state as the photoreactive precursor, and a dissociative model previously proposed to explain the photostereochemistry of d6 metal complexes has been useful also for this d5 system. © 1983 American Chemical Society.
Persistent Identifierhttp://hdl.handle.net/10722/168349
ISSN
2015 Impact Factor: 4.82
2015 SCImago Journal Rankings: 1.873

 

DC FieldValueLanguage
dc.contributor.authorPoon, CKen_US
dc.contributor.authorLau, TCen_US
dc.contributor.authorChe, CMen_US
dc.date.accessioned2012-10-08T03:17:53Z-
dc.date.available2012-10-08T03:17:53Z-
dc.date.issued1983en_US
dc.identifier.citationInorganic Chemistry, 1983, v. 22 n. 26, p. 3893-3898en_US
dc.identifier.issn0020-1669en_US
dc.identifier.urihttp://hdl.handle.net/10722/168349-
dc.description.abstractThe electronic absorption spectra of an extensive series of tetraamine complexes of the type trans-[RuLX2]+ (X = Cl, Br, or I) have been analyzed. In general, two ligand-to-metal charge-transfer (CTTM) transitions of (pπ)x → dπ* origin are observed. The wavelength of the lowest energy band increases gradually with increasing chelation and steric congestion of the amine ligand L around the ruthenium(III) ion. The splitting of the (pπ)x → dπ* transition is largest for the two sterically congested teta and tetb complexes, where teta and tetb represent C-meso- and C-rac-5,5,7,12,12,14-hexa-methyl-1,4,8,11-tetraazacyclotetradecane, respectively, but decreases with the nature of X, Cl > Br > I. The spectra of trans-[Ru(cyclam)X2]X (X = Cl or Br) have been resolved at low temperature (∼30 K), and (pσ)x → dπ* transitions have been assigned to some of these resolved bands. Photochemistry of trans-[RuLIX]+ (L = (en)2, X = Cl, Br, or I; L = 2,3,2-tet or cyclam, X = I; en, 2,3,2-tet, and cyclam represent ethane-1,2-diamine, 3,7-diazanonane-1,9-diamine, and 1,4,8,11-tetraazacyclotetradecane, respectively) has been investigated. Irradiation at the lowest CTTM band (λirr > 500 nm) leads to stereoretentive aquation of X- with quantum yields independent of X but decreasing with increasing chelation of L. Domination of the RuII-I• entity in the CTTM excited state has been discussed. Irradiation of the second CTTM band leads to photoaquation with concomitant stereochemical change. The results are interpreted in terms of a quartet ligand field state as the photoreactive precursor, and a dissociative model previously proposed to explain the photostereochemistry of d6 metal complexes has been useful also for this d5 system. © 1983 American Chemical Society.en_US
dc.languageengen_US
dc.publisherAmerican Chemical Society. The Journal's web site is located at http://pubs.acs.org/icen_US
dc.relation.ispartofInorganic Chemistryen_US
dc.titleStructural and mechanistic studies of coordination compounds. 36. Electronic spectra and photochemistry of some trans-(tetraamine)ruthenium(III) complexesen_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.scopuseid_2-s2.0-5744242073en_US
dc.identifier.volume22en_US
dc.identifier.issue26en_US
dc.identifier.spage3893en_US
dc.identifier.epage3898en_US
dc.publisher.placeUnited Statesen_US
dc.identifier.scopusauthoridPoon, CK=7202673504en_US
dc.identifier.scopusauthoridLau, TC=7102222310en_US
dc.identifier.scopusauthoridChe, CM=7102442791en_US

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