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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
Title | 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 |
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Authors | |
Issue Date | 1999 |
Publisher | American 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? |
Abstract | Ruthenium(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 Identifier | http://hdl.handle.net/10722/167247 |
ISSN | 2023 Impact Factor: 2.5 2023 SCImago Journal Rankings: 0.654 |
ISI Accession Number ID | |
References |
DC Field | Value | Language |
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dc.contributor.author | Choi, MY | en_US |
dc.contributor.author | Chan, MCW | en_US |
dc.contributor.author | Zhang, S | en_US |
dc.contributor.author | Cheung, KK | en_US |
dc.contributor.author | Che, CM | en_US |
dc.contributor.author | Wong, KY | en_US |
dc.date.accessioned | 2012-10-08T03:04:52Z | - |
dc.date.available | 2012-10-08T03:04:52Z | - |
dc.date.issued | 1999 | en_US |
dc.identifier.citation | Organometallics, 1999, v. 18 n. 11, p. 2074-2080 | en_US |
dc.identifier.issn | 0276-7333 | en_US |
dc.identifier.uri | http://hdl.handle.net/10722/167247 | - |
dc.description.abstract | Ruthenium(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.language | eng | en_US |
dc.publisher | American Chemical Society. The Journal's web site is located at http://pubs.acs.org/organometallics | en_US |
dc.relation.ispartof | Organometallics | en_US |
dc.title | 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 | 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.doi | 10.1021/om990009d | - |
dc.identifier.scopus | eid_2-s2.0-0000014903 | en_US |
dc.identifier.hkuros | 44190 | - |
dc.relation.references | http://www.scopus.com/mlt/select.url?eid=2-s2.0-0000014903&selection=ref&src=s&origin=recordpage | en_US |
dc.identifier.volume | 18 | en_US |
dc.identifier.issue | 11 | en_US |
dc.identifier.spage | 2074 | en_US |
dc.identifier.epage | 2080 | en_US |
dc.identifier.isi | WOS:000080587400008 | - |
dc.publisher.place | United States | en_US |
dc.identifier.scopusauthorid | Choi, MY=36929153100 | en_US |
dc.identifier.scopusauthorid | Chan, MCW=7402598116 | en_US |
dc.identifier.scopusauthorid | Zhang, S=7409376552 | en_US |
dc.identifier.scopusauthorid | Cheung, KK=7402406613 | en_US |
dc.identifier.scopusauthorid | Che, CM=7102442791 | en_US |
dc.identifier.scopusauthorid | Wong, KY=7404760030 | en_US |
dc.identifier.issnl | 0276-7333 | - |