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Article: Spectroscopic studies and structures of trans-ruthenium(II) and ruthenium(III) bis(cyanide) complexes supported by a tetradentate macrocyclic tertiary amine ligand

TitleSpectroscopic studies and structures of trans-ruthenium(II) and ruthenium(III) bis(cyanide) complexes supported by a tetradentate macrocyclic tertiary amine ligand
Authors
Issue Date2008
PublisherAmerican Chemical Society. The Journal's web site is located at http://pubs.acs.org/ic
Citation
Inorganic Chemistry, 2008, v. 47 n. 22, p. 10308-10316 How to Cite?
Abstracttrans-[Ru(16-TMC)(C≡N) 2] (1; 16-TMC = 1,5,9,13- tetramethyl-1,5,9,13-tetraazacyclohexadecane) was prepared by the reaction of trans-[Ru(16-TMC)Cl 2]Cl with KCN in the presence of zinc powder. The oxidation of 1 with bromine gave trans-[Ru(16-TMC)(C≡N) 2] + isolated as PF 6 salt (2·PF 6). The Ru-C/C-N distances are 2.061(4)/1.130(5) and 2.069(5)/1.140(7) Å for 1 and 2, respectively. Both complexes show a Ru(III/II) couple at 0.10 V versus FeCp 2 +/0. The UV-vis absorption spectrum of 1 is dominated by an intense high-energy absorption at λ max = 230 nm, which is mainly originated from d π(Ru II) → π*(N≡C-Ru-C≡N) charge-transfer transition. Complex 2 shows intense absorption bands at λ max ≤ 228 nm and weaker vibronically structured absorption bands with peak maxima at 315-441 nm (ε max ≈ (5-8) × 10 2 dm 3 mol -1 cm -1), which are assigned to dπ(Ru III) → π*(N≡C-Ru-C≡N) and σ( -C≡N) → d(Ru III) charge-transfer transition, respectively. Density functional theory and time-dependent density-functional theory calculations have been performed on trans-[(NH 3) 4Ru(C≡N) 2] (1′) and trans-[(NH 3) 4Ru(C≡N) 2] + (2′) to examine the Ru-cyanide interaction and the nature of associated electronic transition(s). The 230 nm band of 1 has been probed by resonance Raman spectroscopy. Simulations of the absorption band and the resonance Raman intensities show that the nominal ν C≡N stretch mode accounts for ca. 66% of the total vibrational reorganization energy. A change of nominal bond order for the cyanide ligand from 3 to 2.5 is estimated upon the electronic excitation. © 2008 American Chemical Society.
Persistent Identifierhttp://hdl.handle.net/10722/168346
ISSN
2015 Impact Factor: 4.82
2015 SCImago Journal Rankings: 1.873
ISI Accession Number ID
References

 

DC FieldValueLanguage
dc.contributor.authorWong, CYen_HK
dc.contributor.authorLee, FWen_HK
dc.contributor.authorChe, CMen_HK
dc.contributor.authorYung, FCen_HK
dc.contributor.authorPhillips, DLen_HK
dc.contributor.authorZhu, Nen_HK
dc.date.accessioned2012-10-08T03:17:50Z-
dc.date.available2012-10-08T03:17:50Z-
dc.date.issued2008en_HK
dc.identifier.citationInorganic Chemistry, 2008, v. 47 n. 22, p. 10308-10316en_HK
dc.identifier.issn0020-1669en_HK
dc.identifier.urihttp://hdl.handle.net/10722/168346-
dc.description.abstracttrans-[Ru(16-TMC)(C≡N) 2] (1; 16-TMC = 1,5,9,13- tetramethyl-1,5,9,13-tetraazacyclohexadecane) was prepared by the reaction of trans-[Ru(16-TMC)Cl 2]Cl with KCN in the presence of zinc powder. The oxidation of 1 with bromine gave trans-[Ru(16-TMC)(C≡N) 2] + isolated as PF 6 salt (2·PF 6). The Ru-C/C-N distances are 2.061(4)/1.130(5) and 2.069(5)/1.140(7) Å for 1 and 2, respectively. Both complexes show a Ru(III/II) couple at 0.10 V versus FeCp 2 +/0. The UV-vis absorption spectrum of 1 is dominated by an intense high-energy absorption at λ max = 230 nm, which is mainly originated from d π(Ru II) → π*(N≡C-Ru-C≡N) charge-transfer transition. Complex 2 shows intense absorption bands at λ max ≤ 228 nm and weaker vibronically structured absorption bands with peak maxima at 315-441 nm (ε max ≈ (5-8) × 10 2 dm 3 mol -1 cm -1), which are assigned to dπ(Ru III) → π*(N≡C-Ru-C≡N) and σ( -C≡N) → d(Ru III) charge-transfer transition, respectively. Density functional theory and time-dependent density-functional theory calculations have been performed on trans-[(NH 3) 4Ru(C≡N) 2] (1′) and trans-[(NH 3) 4Ru(C≡N) 2] + (2′) to examine the Ru-cyanide interaction and the nature of associated electronic transition(s). The 230 nm band of 1 has been probed by resonance Raman spectroscopy. Simulations of the absorption band and the resonance Raman intensities show that the nominal ν C≡N stretch mode accounts for ca. 66% of the total vibrational reorganization energy. A change of nominal bond order for the cyanide ligand from 3 to 2.5 is estimated upon the electronic excitation. © 2008 American Chemical Society.en_HK
dc.languageengen_US
dc.publisherAmerican Chemical Society. The Journal's web site is located at http://pubs.acs.org/icen_HK
dc.relation.ispartofInorganic Chemistryen_HK
dc.subject.meshAmines - Chemical Synthesis - Chemistryen_US
dc.subject.meshCrystallography, X-Rayen_US
dc.subject.meshCyanides - Chemical Synthesis - Chemistryen_US
dc.subject.meshElectrochemistryen_US
dc.subject.meshLigandsen_US
dc.subject.meshMacrocyclic Compounds - Chemical Synthesis - Chemistryen_US
dc.subject.meshOrganometallic Compounds - Chemical Synthesis - Chemistryen_US
dc.subject.meshRuthenium - Chemistryen_US
dc.subject.meshSpectrophotometry, Ultravioleten_US
dc.subject.meshSpectrum Analysis, Ramanen_US
dc.titleSpectroscopic studies and structures of trans-ruthenium(II) and ruthenium(III) bis(cyanide) complexes supported by a tetradentate macrocyclic tertiary amine liganden_HK
dc.typeArticleen_HK
dc.identifier.emailChe, CM: cmche@hku.hken_HK
dc.identifier.emailPhillips, DL: phillips@hku.hken_HK
dc.identifier.emailZhu, N: nzhu@hkucc.hku.hken_HK
dc.identifier.authorityChe, CM=rp00670en_HK
dc.identifier.authorityPhillips, DL=rp00770en_HK
dc.identifier.authorityZhu, N=rp00845en_HK
dc.description.naturelink_to_subscribed_fulltexten_US
dc.identifier.doi10.1021/ic800743aen_HK
dc.identifier.pmid18850698-
dc.identifier.scopuseid_2-s2.0-57149093628en_HK
dc.identifier.hkuros155710-
dc.relation.referenceshttp://www.scopus.com/mlt/select.url?eid=2-s2.0-57149093628&selection=ref&src=s&origin=recordpageen_HK
dc.identifier.volume47en_HK
dc.identifier.issue22en_HK
dc.identifier.spage10308en_HK
dc.identifier.epage10316en_HK
dc.identifier.isiWOS:000260791100024-
dc.publisher.placeUnited Statesen_HK
dc.identifier.scopusauthoridWong, CY=7404954160en_HK
dc.identifier.scopusauthoridLee, FW=7403111574en_HK
dc.identifier.scopusauthoridChe, CM=7102442791en_HK
dc.identifier.scopusauthoridYung, FC=25724810100en_HK
dc.identifier.scopusauthoridPhillips, DL=7404519365en_HK
dc.identifier.scopusauthoridZhu, N=7201449530en_HK

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