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- Publisher Website: 10.1002/chem.200701563
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- PMID: 18478515
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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
Title | 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 |
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Authors | |
Keywords | Density functional calculations Electronic structure High-valent compounds Iron Oxo ligands |
Issue Date | 2008 |
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, 2008, v. 14 n. 18, p. 5495-5506 How to Cite? |
Abstract | Density 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 Identifier | http://hdl.handle.net/10722/69465 |
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 | Tong, GSM | en_HK |
dc.contributor.author | Wong, ELM | en_HK |
dc.contributor.author | Che, CM | en_HK |
dc.date.accessioned | 2010-09-06T06:13:54Z | - |
dc.date.available | 2010-09-06T06:13:54Z | - |
dc.date.issued | 2008 | en_HK |
dc.identifier.citation | Chemistry - A European Journal, 2008, v. 14 n. 18, p. 5495-5506 | en_HK |
dc.identifier.issn | 0947-6539 | en_HK |
dc.identifier.uri | http://hdl.handle.net/10722/69465 | - |
dc.description.abstract | Density 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.language | eng | en_HK |
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 | Density functional calculations | en_HK |
dc.subject | Electronic structure | en_HK |
dc.subject | High-valent compounds | en_HK |
dc.subject | Iron | en_HK |
dc.subject | Oxo ligands | en_HK |
dc.subject.mesh | Amines - chemistry | - |
dc.subject.mesh | Iron - chemistry | - |
dc.subject.mesh | Osmium - chemistry | - |
dc.subject.mesh | Ruthenium - chemistry | - |
dc.subject.mesh | Spectrometry, Mass, Electrospray Ionization - methods | - |
dc.title | 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 | en_HK |
dc.type | Article | en_HK |
dc.identifier.openurl | http://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+spectrometry | en_HK |
dc.identifier.email | Tong, GSM:tongsm@hkucc.hku.hk | en_HK |
dc.identifier.email | Wong, ELM:wongella@hku.hk | en_HK |
dc.identifier.email | Che, CM:cmche@hku.hk | en_HK |
dc.identifier.authority | Tong, GSM=rp00790 | en_HK |
dc.identifier.authority | Wong, ELM=rp00807 | en_HK |
dc.identifier.authority | Che, CM=rp00670 | en_HK |
dc.description.nature | link_to_subscribed_fulltext | - |
dc.identifier.doi | 10.1002/chem.200701563 | en_HK |
dc.identifier.pmid | 18478515 | - |
dc.identifier.scopus | eid_2-s2.0-53849105800 | en_HK |
dc.identifier.hkuros | 142335 | en_HK |
dc.relation.references | http://www.scopus.com/mlt/select.url?eid=2-s2.0-53849105800&selection=ref&src=s&origin=recordpage | en_HK |
dc.identifier.volume | 14 | en_HK |
dc.identifier.issue | 18 | en_HK |
dc.identifier.spage | 5495 | en_HK |
dc.identifier.epage | 5506 | en_HK |
dc.identifier.isi | WOS:000257574800014 | - |
dc.publisher.place | Germany | en_HK |
dc.identifier.scopusauthorid | Tong, GSM=7102328656 | en_HK |
dc.identifier.scopusauthorid | Wong, ELM=8944839700 | en_HK |
dc.identifier.scopusauthorid | Che, CM=7102442791 | en_HK |
dc.identifier.issnl | 0947-6539 | - |