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Article: Ruthenium(II) σ-acetylide and carbene complexes supported by the terpyridine-bipyridine ligand set: Structural, spectroscopic, and photochemical studies

TitleRuthenium(II) σ-acetylide and carbene complexes supported by the terpyridine-bipyridine ligand set: Structural, spectroscopic, and photochemical studies
Authors
Issue Date2004
PublisherAmerican Chemical Society. The Journal's web site is located at http://pubs.acs.org/organometallics
Citation
Organometallics, 2004, v. 23 n. 10, p. 2263-2272 How to Cite?
AbstractA series of acetylide- and carbene-ruthenium complexes containing polypyridine ligands, [(tpy(bpy)RuC=CR]+ (tpy = 2,2′:6′, 2″-terpyridine, bpy = 2,2′-bipyridine; R = C6H 4F-4 (1), C6H4Cl-4 (2), C6H 5 (3), C6H4Me-4 (4), C6H 4OMe-4 (5), t-Bu (6), (C6H4C≡C) nC6H5 [n = 1 (7) and 2 (8)]) and [(tpy)(bpy)Ru=C(OMe)(CH2R)]2+ (R = C6H 4OMe-4 (9), t-Bu (10)) have been prepared. The molecular structures of 4(PF6), 5(PF6), and 9(ClO4)2 reveal Ru-C distances of 2.025(9), 2.025(7), and 1.933(6) Å, respectively. The Ru(III/II) oxidation waves are irreversible for 1-8 (Epa = 0.15-0.26 V vs FeCp2 +/0) but reversible for 9 and 10 (E 1/2 = 0.99 and 1.00 V, respectively). The absorption bands in the visible region for 1-8 (λmax = 502-526 nm) and 9 and 10 (λmax ca. 410 nm) are assigned as dπ(Ru II) → π*(polypyridine) MLCT transitions. Complexes 1-8 weakly emit at λmax = 748-786 nm in CH3CN solution at 298 K (λex = 550 nm). Complexes 9 and 10 are nonemissive in CH2Cl2 solution at 298 K, but in glassy n-butyronitrile at 77 K, excitation at λ = 415 nm produces emission at λmax = 597 and 615 nm, respectively. These emissions are tentatively ascribed as dπ(RuII) → π*(polypyridyl) 3MLCT in nature. The carbene derivatives 9 and 10 undergo photochemical reactions upon irradiation in solution, and [(tpy)(bpy)RuN≡CCH3]2+ and 4-methoxybenzaldehyde were isolated from the photolysis of 9 in CH3CN.
Persistent Identifierhttp://hdl.handle.net/10722/167957
ISSN
2015 Impact Factor: 4.186
2015 SCImago Journal Rankings: 2.043
ISI Accession Number ID
References

 

DC FieldValueLanguage
dc.contributor.authorWong, CYen_HK
dc.contributor.authorChan, MCWen_HK
dc.contributor.authorZhu, Nen_HK
dc.contributor.authorChe, CMen_HK
dc.date.accessioned2012-10-08T03:13:25Z-
dc.date.available2012-10-08T03:13:25Z-
dc.date.issued2004en_HK
dc.identifier.citationOrganometallics, 2004, v. 23 n. 10, p. 2263-2272en_HK
dc.identifier.issn0276-7333en_HK
dc.identifier.urihttp://hdl.handle.net/10722/167957-
dc.description.abstractA series of acetylide- and carbene-ruthenium complexes containing polypyridine ligands, [(tpy(bpy)RuC=CR]+ (tpy = 2,2′:6′, 2″-terpyridine, bpy = 2,2′-bipyridine; R = C6H 4F-4 (1), C6H4Cl-4 (2), C6H 5 (3), C6H4Me-4 (4), C6H 4OMe-4 (5), t-Bu (6), (C6H4C≡C) nC6H5 [n = 1 (7) and 2 (8)]) and [(tpy)(bpy)Ru=C(OMe)(CH2R)]2+ (R = C6H 4OMe-4 (9), t-Bu (10)) have been prepared. The molecular structures of 4(PF6), 5(PF6), and 9(ClO4)2 reveal Ru-C distances of 2.025(9), 2.025(7), and 1.933(6) Å, respectively. The Ru(III/II) oxidation waves are irreversible for 1-8 (Epa = 0.15-0.26 V vs FeCp2 +/0) but reversible for 9 and 10 (E 1/2 = 0.99 and 1.00 V, respectively). The absorption bands in the visible region for 1-8 (λmax = 502-526 nm) and 9 and 10 (λmax ca. 410 nm) are assigned as dπ(Ru II) → π*(polypyridine) MLCT transitions. Complexes 1-8 weakly emit at λmax = 748-786 nm in CH3CN solution at 298 K (λex = 550 nm). Complexes 9 and 10 are nonemissive in CH2Cl2 solution at 298 K, but in glassy n-butyronitrile at 77 K, excitation at λ = 415 nm produces emission at λmax = 597 and 615 nm, respectively. These emissions are tentatively ascribed as dπ(RuII) → π*(polypyridyl) 3MLCT in nature. The carbene derivatives 9 and 10 undergo photochemical reactions upon irradiation in solution, and [(tpy)(bpy)RuN≡CCH3]2+ and 4-methoxybenzaldehyde were isolated from the photolysis of 9 in CH3CN.en_HK
dc.languageengen_US
dc.publisherAmerican Chemical Society. The Journal's web site is located at http://pubs.acs.org/organometallicsen_HK
dc.relation.ispartofOrganometallicsen_HK
dc.titleRuthenium(II) σ-acetylide and carbene complexes supported by the terpyridine-bipyridine ligand set: Structural, spectroscopic, and photochemical studiesen_HK
dc.typeArticleen_HK
dc.identifier.emailZhu, N: nzhu@hkucc.hku.hken_HK
dc.identifier.emailChe, CM: cmche@hku.hken_HK
dc.identifier.authorityZhu, N=rp00845en_HK
dc.identifier.authorityChe, CM=rp00670en_HK
dc.description.naturelink_to_subscribed_fulltexten_US
dc.identifier.doi10.1021/om034379ken_HK
dc.identifier.scopuseid_2-s2.0-2542493095en_HK
dc.identifier.hkuros90922-
dc.relation.referenceshttp://www.scopus.com/mlt/select.url?eid=2-s2.0-2542493095&selection=ref&src=s&origin=recordpageen_HK
dc.identifier.volume23en_HK
dc.identifier.issue10en_HK
dc.identifier.spage2263en_HK
dc.identifier.epage2272en_HK
dc.identifier.isiWOS:000221231100010-
dc.publisher.placeUnited Statesen_HK
dc.identifier.scopusauthoridWong, CY=7404954160en_HK
dc.identifier.scopusauthoridChan, MCW=7402598116en_HK
dc.identifier.scopusauthoridZhu, N=7201449530en_HK
dc.identifier.scopusauthoridChe, CM=7102442791en_HK

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