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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

TitleSpectral, structural, and electrochemical properties of ruthenium porphyrin diaryl and aryl(alkoxyrcarbonyl) carbene complexes: Influence of carbene substituents, porphyrin substituents, and trans-axial ligands
Authors
KeywordsCarbene ligands
Electrochemistry
Macrocyclic ligands
Porphyrins
Ruthonium
Issue Date2004
PublisherWiley - 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?
AbstractA 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 Identifierhttp://hdl.handle.net/10722/168002
ISSN
2015 Impact Factor: 5.771
2015 SCImago Journal Rankings: 2.323
ISI Accession Number ID
References

 

DC FieldValueLanguage
dc.contributor.authorLi, Yen_HK
dc.contributor.authorHuang, JSen_HK
dc.contributor.authorXu, GBen_HK
dc.contributor.authorZhu, Nen_HK
dc.contributor.authorZhou, ZYen_HK
dc.contributor.authorChe, CMen_HK
dc.contributor.authorWong, KYen_HK
dc.date.accessioned2012-10-08T03:13:58Z-
dc.date.available2012-10-08T03:13:58Z-
dc.date.issued2004en_HK
dc.identifier.citationChemistry - A European Journal, 2004, v. 10 n. 14, p. 3486-3502en_HK
dc.identifier.issn0947-6539en_HK
dc.identifier.urihttp://hdl.handle.net/10722/168002-
dc.description.abstractA 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.languageengen_US
dc.publisherWiley - V C H Verlag GmbH & Co KGaA. The Journal's web site is located at http://www.wiley-vch.de/home/chemistryen_HK
dc.relation.ispartofChemistry - A European Journalen_HK
dc.subjectCarbene ligandsen_HK
dc.subjectElectrochemistryen_HK
dc.subjectMacrocyclic ligandsen_HK
dc.subjectPorphyrinsen_HK
dc.subjectRuthoniumen_HK
dc.titleSpectral, structural, and electrochemical properties of ruthenium porphyrin diaryl and aryl(alkoxyrcarbonyl) carbene complexes: Influence of carbene substituents, porphyrin substituents, and trans-axial ligandsen_HK
dc.typeArticleen_HK
dc.identifier.emailHuang, JS: jshuang@hku.hken_HK
dc.identifier.emailZhu, N: nzhu@hkucc.hku.hken_HK
dc.identifier.emailChe, CM: cmche@hku.hken_HK
dc.identifier.authorityHuang, JS=rp00709en_HK
dc.identifier.authorityZhu, N=rp00845en_HK
dc.identifier.authorityChe, CM=rp00670en_HK
dc.description.naturelink_to_subscribed_fulltexten_US
dc.identifier.doi10.1002/chem.200305758en_HK
dc.identifier.pmid15252795-
dc.identifier.scopuseid_2-s2.0-3242878878en_HK
dc.identifier.hkuros94242-
dc.relation.referenceshttp://www.scopus.com/mlt/select.url?eid=2-s2.0-3242878878&selection=ref&src=s&origin=recordpageen_HK
dc.identifier.volume10en_HK
dc.identifier.issue14en_HK
dc.identifier.spage3486en_HK
dc.identifier.epage3502en_HK
dc.identifier.isiWOS:000222888400016-
dc.publisher.placeGermanyen_HK
dc.identifier.scopusauthoridLi, Y=35187394200en_HK
dc.identifier.scopusauthoridHuang, JS=7407192639en_HK
dc.identifier.scopusauthoridXu, GB=8427026200en_HK
dc.identifier.scopusauthoridZhu, N=7201449530en_HK
dc.identifier.scopusauthoridZhou, ZY=7406096262en_HK
dc.identifier.scopusauthoridChe, CM=7102442791en_HK
dc.identifier.scopusauthoridWong, KY=7404760030en_HK

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