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Article: Structural and mechanistic studies of coordination compounds. 36. Electronic spectra and photochemistry of some trans-(tetraamine)ruthenium(III) complexes
Title | Structural and mechanistic studies of coordination compounds. 36. Electronic spectra and photochemistry of some trans-(tetraamine)ruthenium(III) complexes |
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Authors | |
Issue Date | 1983 |
Publisher | American 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? |
Abstract | The 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 Identifier | http://hdl.handle.net/10722/168349 |
ISSN | 2023 Impact Factor: 4.3 2023 SCImago Journal Rankings: 0.928 |
ISI Accession Number ID |
DC Field | Value | Language |
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dc.contributor.author | Poon, CK | en_US |
dc.contributor.author | Lau, TC | en_US |
dc.contributor.author | Che, CM | en_US |
dc.date.accessioned | 2012-10-08T03:17:53Z | - |
dc.date.available | 2012-10-08T03:17:53Z | - |
dc.date.issued | 1983 | en_US |
dc.identifier.citation | Inorganic Chemistry, 1983, v. 22 n. 26, p. 3893-3898 | en_US |
dc.identifier.issn | 0020-1669 | en_US |
dc.identifier.uri | http://hdl.handle.net/10722/168349 | - |
dc.description.abstract | The 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.language | eng | en_US |
dc.publisher | American Chemical Society. The Journal's web site is located at http://pubs.acs.org/ic | en_US |
dc.relation.ispartof | Inorganic Chemistry | en_US |
dc.title | Structural and mechanistic studies of coordination compounds. 36. Electronic spectra and photochemistry of some trans-(tetraamine)ruthenium(III) complexes | en_US |
dc.type | Article | en_US |
dc.identifier.email | Che, CM:cmche@hku.hk | en_US |
dc.identifier.authority | Che, CM=rp00670 | en_US |
dc.description.nature | link_to_subscribed_fulltext | en_US |
dc.identifier.scopus | eid_2-s2.0-5744242073 | en_US |
dc.identifier.volume | 22 | en_US |
dc.identifier.issue | 26 | en_US |
dc.identifier.spage | 3893 | en_US |
dc.identifier.epage | 3898 | en_US |
dc.identifier.isi | WOS:A1983RX27500015 | - |
dc.publisher.place | United States | en_US |
dc.identifier.scopusauthorid | Poon, CK=7202673504 | en_US |
dc.identifier.scopusauthorid | Lau, TC=7102222310 | en_US |
dc.identifier.scopusauthorid | Che, CM=7102442791 | en_US |
dc.identifier.issnl | 0020-1669 | - |