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Article: Density functional theory study of trans-dioxo complexes of iron, ruthenium, and osmium with saturated amine ligands, trans-[M(O) 2(NH3)2(NMeH2)2] 2+ (M = Fe, Ru, Os), and detection of [Fe(qpy)(O)2] n+ (n = 1, 2) by high-resolution ESI mass spectrometry

TitleDensity functional theory study of trans-dioxo complexes of iron, ruthenium, and osmium with saturated amine ligands, trans-[M(O) 2(NH3)2(NMeH2)2] 2+ (M = Fe, Ru, Os), and detection of [Fe(qpy)(O)2] n+ (n = 1, 2) by high-resolution ESI mass spectrometry
Authors
KeywordsDensity functional calculations
Electronic structure
High-valent compounds
Iron
Oxo ligands
Issue Date2008
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, 2008, v. 14 n. 18, p. 5495-5506 How to Cite?
AbstractDensity functional theory (DFT) calculations on trans-dioxo metal complexes containing saturated amine ligands, trans-[M(O)2(NH 3)2-(NMeH2)2]2+ (M = Fe, Ru, Os), were performed with different types of density functionals (DFs): 1)pure generalized gradient approximations (pure GGAs): PW91, BP86, and OLYP; 2) meta-GGAs: VSXC and HCTH407; and 3) hybrid DFs: B3LYP and PBE1PBE. With pure GGAs and meta-GGAs, a singlet d2 ground state for trans-[Fe(O) 2(NH3)2(NMeH2)2] 2+ was obtained, but a quintet ground state was predicted by the hybrid DFs B3LYP and PBE1PBE. The lowest transition energies in water were calculated to be at λ ≈ 509 and 515 nm in the respective ground-state geometries from PW91 and B3LYP calculations. The nature of this transition is dependent on the DFs used: a ligand-to-metal charge-transfer (LMCT) transition with PW91, but a π(Fe-O)→π*-(Fe-O) transition with B3LYP, in which it and π* are the bonding and antibonding combinations between the dπ(Fe) and Pπ(O2-) orbitais. The FeVI/V reduction potential of trans-[Fe(O)2-(NH 3)2(NMeH2)2]2+ was estimated to be +1.30 V versus NHE based on PW91 results. The [Fe(qpy)(O) 2]n+ (qpy = 2,2′:6′,2″:6″, 2‴:6‴,2-quinque-pyridine; N = 1 and 2) ions, tentatively assigned to dioxo iron(V) and dioxo iron(VI), respectively, were detected in the gas phase by high-resolution ESI-MS spectroscopy. © 2008 Wiley-VCH Verlag GmbH & Co. KGaA.
Persistent Identifierhttp://hdl.handle.net/10722/69465
ISSN
2015 Impact Factor: 5.771
2015 SCImago Journal Rankings: 2.323
ISI Accession Number ID
References

 

DC FieldValueLanguage
dc.contributor.authorTong, GSMen_HK
dc.contributor.authorWong, ELMen_HK
dc.contributor.authorChe, CMen_HK
dc.date.accessioned2010-09-06T06:13:54Z-
dc.date.available2010-09-06T06:13:54Z-
dc.date.issued2008en_HK
dc.identifier.citationChemistry - A European Journal, 2008, v. 14 n. 18, p. 5495-5506en_HK
dc.identifier.issn0947-6539en_HK
dc.identifier.urihttp://hdl.handle.net/10722/69465-
dc.description.abstractDensity functional theory (DFT) calculations on trans-dioxo metal complexes containing saturated amine ligands, trans-[M(O)2(NH 3)2-(NMeH2)2]2+ (M = Fe, Ru, Os), were performed with different types of density functionals (DFs): 1)pure generalized gradient approximations (pure GGAs): PW91, BP86, and OLYP; 2) meta-GGAs: VSXC and HCTH407; and 3) hybrid DFs: B3LYP and PBE1PBE. With pure GGAs and meta-GGAs, a singlet d2 ground state for trans-[Fe(O) 2(NH3)2(NMeH2)2] 2+ was obtained, but a quintet ground state was predicted by the hybrid DFs B3LYP and PBE1PBE. The lowest transition energies in water were calculated to be at λ ≈ 509 and 515 nm in the respective ground-state geometries from PW91 and B3LYP calculations. The nature of this transition is dependent on the DFs used: a ligand-to-metal charge-transfer (LMCT) transition with PW91, but a π(Fe-O)→π*-(Fe-O) transition with B3LYP, in which it and π* are the bonding and antibonding combinations between the dπ(Fe) and Pπ(O2-) orbitais. The FeVI/V reduction potential of trans-[Fe(O)2-(NH 3)2(NMeH2)2]2+ was estimated to be +1.30 V versus NHE based on PW91 results. The [Fe(qpy)(O) 2]n+ (qpy = 2,2′:6′,2″:6″, 2‴:6‴,2-quinque-pyridine; N = 1 and 2) ions, tentatively assigned to dioxo iron(V) and dioxo iron(VI), respectively, were detected in the gas phase by high-resolution ESI-MS spectroscopy. © 2008 Wiley-VCH Verlag GmbH & Co. KGaA.en_HK
dc.languageengen_HK
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.subjectDensity functional calculationsen_HK
dc.subjectElectronic structureen_HK
dc.subjectHigh-valent compoundsen_HK
dc.subjectIronen_HK
dc.subjectOxo ligandsen_HK
dc.subject.meshAmines - chemistry-
dc.subject.meshIron - chemistry-
dc.subject.meshOsmium - chemistry-
dc.subject.meshRuthenium - chemistry-
dc.subject.meshSpectrometry, Mass, Electrospray Ionization - methods-
dc.titleDensity functional theory study of trans-dioxo complexes of iron, ruthenium, and osmium with saturated amine ligands, trans-[M(O) 2(NH3)2(NMeH2)2] 2+ (M = Fe, Ru, Os), and detection of [Fe(qpy)(O)2] n+ (n = 1, 2) by high-resolution ESI mass spectrometryen_HK
dc.typeArticleen_HK
dc.identifier.openurlhttp://library.hku.hk:4550/resserv?sid=HKU:IR&issn=0947-6539&volume=14&issue=18&spage=5495&epage=5506&date=2008&atitle=Density+functional+theory+study+of+trans-dioxo+complexes+of+iron,+ruthenium,+and+osmium+with+saturated+amine+ligands,+trans-[M(O)+2(NH3)2(NMeH2)2]+2++(M=Fe,+Ru,+Os),+and+detection+of+[Fe(qpy)(O)2]+n++(n=1,+2)+by+high-resolution+ESI+mass+spectrometryen_HK
dc.identifier.emailTong, GSM:tongsm@hkucc.hku.hken_HK
dc.identifier.emailWong, ELM:wongella@hku.hken_HK
dc.identifier.emailChe, CM:cmche@hku.hken_HK
dc.identifier.authorityTong, GSM=rp00790en_HK
dc.identifier.authorityWong, ELM=rp00807en_HK
dc.identifier.authorityChe, CM=rp00670en_HK
dc.description.naturelink_to_subscribed_fulltext-
dc.identifier.doi10.1002/chem.200701563en_HK
dc.identifier.pmid18478515-
dc.identifier.scopuseid_2-s2.0-53849105800en_HK
dc.identifier.hkuros142335en_HK
dc.relation.referenceshttp://www.scopus.com/mlt/select.url?eid=2-s2.0-53849105800&selection=ref&src=s&origin=recordpageen_HK
dc.identifier.volume14en_HK
dc.identifier.issue18en_HK
dc.identifier.spage5495en_HK
dc.identifier.epage5506en_HK
dc.identifier.isiWOS:000257574800014-
dc.publisher.placeGermanyen_HK
dc.identifier.scopusauthoridTong, GSM=7102328656en_HK
dc.identifier.scopusauthoridWong, ELM=8944839700en_HK
dc.identifier.scopusauthoridChe, CM=7102442791en_HK

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