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Article: Spectral, structural, and electrochemical properties of ruthenium porphyrin diaryl and aryl(alkoxyrcarbonyl) carbene complexes: Influence of carbene substituents, porphyrin substituents, and trans-axial ligands
Title | Spectral, structural, and electrochemical properties of ruthenium porphyrin diaryl and aryl(alkoxyrcarbonyl) carbene complexes: Influence of carbene substituents, porphyrin substituents, and trans-axial ligands |
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Authors | |
Keywords | Carbene ligands Electrochemistry Macrocyclic ligands Porphyrins Ruthonium |
Issue Date | 2004 |
Publisher | Wiley - V C H Verlag GmbH & Co KGaA. The Journal's web site is located at http://www.wiley-vch.de/home/chemistry |
Citation | Chemistry - A European Journal, 2004, v. 10 n. 14, p. 3486-3502 How to Cite? |
Abstract | A wide variety of ruthenium porphyrin carbene complexes, including [Ru(tpfpp)(CR 1R 2)] (CR 1R 2 = C(p-C 6H 4Cl) 2 1b, C(p-C 6H 4Me) 2 1e, C(p-C 6H 4OMe) 2 1d, C(CO 2Me) 2 1e, C(p-C 6H 4NO 2)CO 2Me 1f, C(p-C 6H 4OMe)CO 2Me 1g, C(CH= CHPh)CO 2CH 2(CH=CH) 2CH 3 1h), [Ru(por)(CPh 2)] (por=tdcpp 2a, 4-Br-tpp 2b, 4-Cl-tpp 2c, 4-F-tpp 2d, tpp 2e, ttp 2f, 4-MeO-tpp 2g, tmp 2h, 3,4,5-MeO-tpp 2i), [Ru(por){C(Ph)CO 2Et}] (por = tdcpp 2j, tmp 2k), [Ru(tpfpp)(CPh 2)(L)1 (L = MeOH 3a, EtSH 3b, Et 2S 3c, Melm 3d, OPPh 3 3e, py 3f), and [Ru(tpfpp){C(Ph)-CO 2R}(MeOH)] (R = CH 2CH=CH 2 4a, Me 4, b, Et 4c), were prepared from the reactions of [Ru(por)(CO)] with diazo compounds N 2CR 1R 2 in dichloromethane and, for 3 and 4, by further treatment with reagents L. A similar reaction of [Os(tpfpp)(CO)] with N 2CPh 2 in dichloromethane followed by treatment with MeIm gave [Os(tpfpp)(CPh 2)(MeIm)] (3d-Os). All these complexes were characterized by 1H NMR, 13C NMR, and UV/Vis spectroscopy, mass spectrometry, and elemental analyses. X-ray crystal structure determinations of 1d, 2a,i, 3a,b, d,e, 4a-c, and 3d-Os revealed Ru=C distances of 1.806(3)-1.876(3) Å and an Os=C distance of 1.902(3) Å. The structure of 1d in the solid state features a unique "bridging" carbene ligand, which results in the formation of a one-dimensional coordination polymer. Cyclic voltammograms of 1a-c,g, 2a-d,g-k, 3b-d, 4a,b, and 3d-Os show a reversible oxidation couple with E 1/2 values in the range of 0.06-0.65 V (vs Cp 2Fe +/0) that is attributable to a metal-centered oxidation. The influence of carbene substituents, porphyrin substituents, and trans-ligands on the Ru=C bond was examined through comparison of the chemical shifts of the pyrrolic protons in the porphyrin macrocycles ( 1H NMR) and the M=C carbon atoms ( 13C NMR), the potentials of the metal-centered oxidation couples, and the Ru=C distances among the various ruthenium porphyrin carbene complexes. A direct comparison among iron, ruthenium, and osmium porphyrin carbene complexes is made. |
Persistent Identifier | http://hdl.handle.net/10722/168002 |
ISSN | 2023 Impact Factor: 3.9 2023 SCImago Journal Rankings: 1.058 |
ISI Accession Number ID | |
References |
DC Field | Value | Language |
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dc.contributor.author | Li, Y | en_HK |
dc.contributor.author | Huang, JS | en_HK |
dc.contributor.author | Xu, GB | en_HK |
dc.contributor.author | Zhu, N | en_HK |
dc.contributor.author | Zhou, ZY | en_HK |
dc.contributor.author | Che, CM | en_HK |
dc.contributor.author | Wong, KY | en_HK |
dc.date.accessioned | 2012-10-08T03:13:58Z | - |
dc.date.available | 2012-10-08T03:13:58Z | - |
dc.date.issued | 2004 | en_HK |
dc.identifier.citation | Chemistry - A European Journal, 2004, v. 10 n. 14, p. 3486-3502 | en_HK |
dc.identifier.issn | 0947-6539 | en_HK |
dc.identifier.uri | http://hdl.handle.net/10722/168002 | - |
dc.description.abstract | A wide variety of ruthenium porphyrin carbene complexes, including [Ru(tpfpp)(CR 1R 2)] (CR 1R 2 = C(p-C 6H 4Cl) 2 1b, C(p-C 6H 4Me) 2 1e, C(p-C 6H 4OMe) 2 1d, C(CO 2Me) 2 1e, C(p-C 6H 4NO 2)CO 2Me 1f, C(p-C 6H 4OMe)CO 2Me 1g, C(CH= CHPh)CO 2CH 2(CH=CH) 2CH 3 1h), [Ru(por)(CPh 2)] (por=tdcpp 2a, 4-Br-tpp 2b, 4-Cl-tpp 2c, 4-F-tpp 2d, tpp 2e, ttp 2f, 4-MeO-tpp 2g, tmp 2h, 3,4,5-MeO-tpp 2i), [Ru(por){C(Ph)CO 2Et}] (por = tdcpp 2j, tmp 2k), [Ru(tpfpp)(CPh 2)(L)1 (L = MeOH 3a, EtSH 3b, Et 2S 3c, Melm 3d, OPPh 3 3e, py 3f), and [Ru(tpfpp){C(Ph)-CO 2R}(MeOH)] (R = CH 2CH=CH 2 4a, Me 4, b, Et 4c), were prepared from the reactions of [Ru(por)(CO)] with diazo compounds N 2CR 1R 2 in dichloromethane and, for 3 and 4, by further treatment with reagents L. A similar reaction of [Os(tpfpp)(CO)] with N 2CPh 2 in dichloromethane followed by treatment with MeIm gave [Os(tpfpp)(CPh 2)(MeIm)] (3d-Os). All these complexes were characterized by 1H NMR, 13C NMR, and UV/Vis spectroscopy, mass spectrometry, and elemental analyses. X-ray crystal structure determinations of 1d, 2a,i, 3a,b, d,e, 4a-c, and 3d-Os revealed Ru=C distances of 1.806(3)-1.876(3) Å and an Os=C distance of 1.902(3) Å. The structure of 1d in the solid state features a unique "bridging" carbene ligand, which results in the formation of a one-dimensional coordination polymer. Cyclic voltammograms of 1a-c,g, 2a-d,g-k, 3b-d, 4a,b, and 3d-Os show a reversible oxidation couple with E 1/2 values in the range of 0.06-0.65 V (vs Cp 2Fe +/0) that is attributable to a metal-centered oxidation. The influence of carbene substituents, porphyrin substituents, and trans-ligands on the Ru=C bond was examined through comparison of the chemical shifts of the pyrrolic protons in the porphyrin macrocycles ( 1H NMR) and the M=C carbon atoms ( 13C NMR), the potentials of the metal-centered oxidation couples, and the Ru=C distances among the various ruthenium porphyrin carbene complexes. A direct comparison among iron, ruthenium, and osmium porphyrin carbene complexes is made. | en_HK |
dc.language | eng | en_US |
dc.publisher | Wiley - V C H Verlag GmbH & Co KGaA. The Journal's web site is located at http://www.wiley-vch.de/home/chemistry | en_HK |
dc.relation.ispartof | Chemistry - A European Journal | en_HK |
dc.subject | Carbene ligands | en_HK |
dc.subject | Electrochemistry | en_HK |
dc.subject | Macrocyclic ligands | en_HK |
dc.subject | Porphyrins | en_HK |
dc.subject | Ruthonium | en_HK |
dc.title | Spectral, structural, and electrochemical properties of ruthenium porphyrin diaryl and aryl(alkoxyrcarbonyl) carbene complexes: Influence of carbene substituents, porphyrin substituents, and trans-axial ligands | en_HK |
dc.type | Article | en_HK |
dc.identifier.email | Huang, JS: jshuang@hku.hk | 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 | Huang, JS=rp00709 | 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 | 10.1002/chem.200305758 | en_HK |
dc.identifier.pmid | 15252795 | - |
dc.identifier.scopus | eid_2-s2.0-3242878878 | en_HK |
dc.identifier.hkuros | 94242 | - |
dc.relation.references | http://www.scopus.com/mlt/select.url?eid=2-s2.0-3242878878&selection=ref&src=s&origin=recordpage | en_HK |
dc.identifier.volume | 10 | en_HK |
dc.identifier.issue | 14 | en_HK |
dc.identifier.spage | 3486 | en_HK |
dc.identifier.epage | 3502 | en_HK |
dc.identifier.isi | WOS:000222888400016 | - |
dc.publisher.place | Germany | en_HK |
dc.identifier.scopusauthorid | Li, Y=35187394200 | en_HK |
dc.identifier.scopusauthorid | Huang, JS=7407192639 | en_HK |
dc.identifier.scopusauthorid | Xu, GB=8427026200 | en_HK |
dc.identifier.scopusauthorid | Zhu, N=7201449530 | en_HK |
dc.identifier.scopusauthorid | Zhou, ZY=7406096262 | en_HK |
dc.identifier.scopusauthorid | Che, CM=7102442791 | en_HK |
dc.identifier.scopusauthorid | Wong, KY=7404760030 | en_HK |
dc.identifier.issnl | 0947-6539 | - |