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Article: MLCT and LMCT transitions in acetylide complexes. structural, spectroscopic, and redox properties of ruthenium(II) and -(III) Bis(σ-arylacetylide) complexes supported by a tetradentate macrocyclic tertiary amine ligand

TitleMLCT and LMCT transitions in acetylide complexes. structural, spectroscopic, and redox properties of ruthenium(II) and -(III) Bis(σ-arylacetylide) complexes supported by a tetradentate macrocyclic tertiary amine ligand
Authors
Issue Date1999
PublisherAmerican Chemical Society. The Journal's web site is located at http://pubs.acs.org/organometallics
Citation
Organometallics, 1999, v. 18 n. 11, p. 2074-2080 How to Cite?
AbstractRuthenium(II) complexes trans-[Ru(16-TMC)(C≡CC6H4X-p2] (X = OMe (1), Me (2), H (3), F (4), Cl (5); 16-TMC = 1,5,9,13-tetramethyl-l,5,9,13-tetraazacyclohexadecane) are prepared by the reaction of [RuIII(16-TMC)Cl2]Cl with the corresponding alkyne and NaOMe in the presence of zinc amalgam. Low v(C≡C) stretching frequencies are observed for 1-5 and are attributed to the σ-donating nature of 16-TMC. The molecular structures of 1, 3, and 5 have been determined by X-ray crystal analyses, which reveal virtually identical Ru-C and C≡ C bond distances (mean 2.076 and 1.194 Å, respectively). The cyclic voltammograms of 1-5 show quasi-reversible RuIII/II and RuIV/III oxidation couples. Oxidative cleavage of the acetylide ligand in 3 by dioxygen affords [Ru( 16-TMC)(C≡CPh)(CO)]+ (6). Ruthenium(III) derivatives trans-[Ru(16-TMC)(C≡CC6H4X-p)2] + are generated in situ by electrochemical oxidation in dichloromethane or by chemical oxidation of 1-5 with Ce(IV). Their UV-visible absorption spectra show a vibronically structured absorption band with λmax at 716-768 nm. The vibrational progressions, which range from 1730 to 1830 cm-1, imply that the electronic transition involves distortion of the acetylide ligand in the excited state. An assignment of pπ(ArC≡C) →dπ*(RuIII) charge transfer is proposed for this transition.
Persistent Identifierhttp://hdl.handle.net/10722/167247
ISSN
2015 Impact Factor: 4.186
2015 SCImago Journal Rankings: 2.043
ISI Accession Number ID
References

 

DC FieldValueLanguage
dc.contributor.authorChoi, MYen_US
dc.contributor.authorChan, MCWen_US
dc.contributor.authorZhang, Sen_US
dc.contributor.authorCheung, KKen_US
dc.contributor.authorChe, CMen_US
dc.contributor.authorWong, KYen_US
dc.date.accessioned2012-10-08T03:04:52Z-
dc.date.available2012-10-08T03:04:52Z-
dc.date.issued1999en_US
dc.identifier.citationOrganometallics, 1999, v. 18 n. 11, p. 2074-2080en_US
dc.identifier.issn0276-7333en_US
dc.identifier.urihttp://hdl.handle.net/10722/167247-
dc.description.abstractRuthenium(II) complexes trans-[Ru(16-TMC)(C≡CC6H4X-p2] (X = OMe (1), Me (2), H (3), F (4), Cl (5); 16-TMC = 1,5,9,13-tetramethyl-l,5,9,13-tetraazacyclohexadecane) are prepared by the reaction of [RuIII(16-TMC)Cl2]Cl with the corresponding alkyne and NaOMe in the presence of zinc amalgam. Low v(C≡C) stretching frequencies are observed for 1-5 and are attributed to the σ-donating nature of 16-TMC. The molecular structures of 1, 3, and 5 have been determined by X-ray crystal analyses, which reveal virtually identical Ru-C and C≡ C bond distances (mean 2.076 and 1.194 Å, respectively). The cyclic voltammograms of 1-5 show quasi-reversible RuIII/II and RuIV/III oxidation couples. Oxidative cleavage of the acetylide ligand in 3 by dioxygen affords [Ru( 16-TMC)(C≡CPh)(CO)]+ (6). Ruthenium(III) derivatives trans-[Ru(16-TMC)(C≡CC6H4X-p)2] + are generated in situ by electrochemical oxidation in dichloromethane or by chemical oxidation of 1-5 with Ce(IV). Their UV-visible absorption spectra show a vibronically structured absorption band with λmax at 716-768 nm. The vibrational progressions, which range from 1730 to 1830 cm-1, imply that the electronic transition involves distortion of the acetylide ligand in the excited state. An assignment of pπ(ArC≡C) →dπ*(RuIII) charge transfer is proposed for this transition.en_US
dc.languageengen_US
dc.publisherAmerican Chemical Society. The Journal's web site is located at http://pubs.acs.org/organometallicsen_US
dc.relation.ispartofOrganometallicsen_US
dc.titleMLCT and LMCT transitions in acetylide complexes. structural, spectroscopic, and redox properties of ruthenium(II) and -(III) Bis(σ-arylacetylide) complexes supported by a tetradentate macrocyclic tertiary amine liganden_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.doi10.1021/om990009d-
dc.identifier.scopuseid_2-s2.0-0000014903en_US
dc.identifier.hkuros44190-
dc.relation.referenceshttp://www.scopus.com/mlt/select.url?eid=2-s2.0-0000014903&selection=ref&src=s&origin=recordpageen_US
dc.identifier.volume18en_US
dc.identifier.issue11en_US
dc.identifier.spage2074en_US
dc.identifier.epage2080en_US
dc.identifier.isiWOS:000080587400008-
dc.publisher.placeUnited Statesen_US
dc.identifier.scopusauthoridChoi, MY=36929153100en_US
dc.identifier.scopusauthoridChan, MCW=7402598116en_US
dc.identifier.scopusauthoridZhang, S=7409376552en_US
dc.identifier.scopusauthoridCheung, KK=7402406613en_US
dc.identifier.scopusauthoridChe, CM=7102442791en_US
dc.identifier.scopusauthoridWong, KY=7404760030en_US

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