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Article: Ruthenium(II) σ-acetylide and carbene complexes supported by the terpyridine-bipyridine ligand set: Structural, spectroscopic, and photochemical studies
Title | Ruthenium(II) σ-acetylide and carbene complexes supported by the terpyridine-bipyridine ligand set: Structural, spectroscopic, and photochemical studies |
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Authors | |
Issue Date | 2004 |
Publisher | American 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? |
Abstract | A 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 Identifier | http://hdl.handle.net/10722/167957 |
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 | Wong, CY | en_HK |
dc.contributor.author | Chan, MCW | en_HK |
dc.contributor.author | Zhu, N | en_HK |
dc.contributor.author | Che, CM | en_HK |
dc.date.accessioned | 2012-10-08T03:13:25Z | - |
dc.date.available | 2012-10-08T03:13:25Z | - |
dc.date.issued | 2004 | en_HK |
dc.identifier.citation | Organometallics, 2004, v. 23 n. 10, p. 2263-2272 | en_HK |
dc.identifier.issn | 0276-7333 | en_HK |
dc.identifier.uri | http://hdl.handle.net/10722/167957 | - |
dc.description.abstract | A 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.language | eng | en_US |
dc.publisher | American Chemical Society. The Journal's web site is located at http://pubs.acs.org/organometallics | en_HK |
dc.relation.ispartof | Organometallics | en_HK |
dc.title | Ruthenium(II) σ-acetylide and carbene complexes supported by the terpyridine-bipyridine ligand set: Structural, spectroscopic, and photochemical studies | en_HK |
dc.type | Article | en_HK |
dc.identifier.email | Zhu, N: nzhu@hkucc.hku.hk | en_HK |
dc.identifier.email | Che, CM: cmche@hku.hk | en_HK |
dc.identifier.authority | Zhu, N=rp00845 | en_HK |
dc.identifier.authority | Che, CM=rp00670 | en_HK |
dc.description.nature | link_to_subscribed_fulltext | en_US |
dc.identifier.doi | 10.1021/om034379k | en_HK |
dc.identifier.scopus | eid_2-s2.0-2542493095 | en_HK |
dc.identifier.hkuros | 90922 | - |
dc.relation.references | http://www.scopus.com/mlt/select.url?eid=2-s2.0-2542493095&selection=ref&src=s&origin=recordpage | en_HK |
dc.identifier.volume | 23 | en_HK |
dc.identifier.issue | 10 | en_HK |
dc.identifier.spage | 2263 | en_HK |
dc.identifier.epage | 2272 | en_HK |
dc.identifier.isi | WOS:000221231100010 | - |
dc.publisher.place | United States | en_HK |
dc.identifier.scopusauthorid | Wong, CY=7404954160 | en_HK |
dc.identifier.scopusauthorid | Chan, MCW=7402598116 | en_HK |
dc.identifier.scopusauthorid | Zhu, N=7201449530 | en_HK |
dc.identifier.scopusauthorid | Che, CM=7102442791 | en_HK |
dc.identifier.issnl | 0276-7333 | - |