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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.
Chemistry. 2008; 14(18):5495-506.C

Abstract

Density functional theory (DFT) calculations on trans-dioxo metal complexes containing saturated amine ligands, trans-[M(O)2(NH3)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 lambda approximately 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 pi(Fe-O)-->pi*(Fe-O) transition with B3LYP, in which pi and pi* are the bonding and antibonding combinations between the dpi(Fe) and ppi(O(2-)) orbitals. The FeVI/V reduction potential of trans-[Fe(O)2(NH3)2NMeH2)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''''-quinquepyridine; 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.

Authors+Show Affiliations

Department of Chemistry and Open Laboratory of Chemical Biology of the Institute of Molecular Technology for Drug Discovery and Synthesis, The University of Hong Kong, Pokfulam Road, Hong Kong.No affiliation info availableNo affiliation info available

Pub Type(s)

Journal Article
Research Support, Non-U.S. Gov't

Language

eng

PubMed ID

18478515

Citation

Tong, Glenna So Ming, et al. "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." Chemistry (Weinheim an Der Bergstrasse, Germany), vol. 14, no. 18, 2008, pp. 5495-506.
Tong GS, Wong EL, Che CM. 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. Chemistry. 2008;14(18):5495-506.
Tong, G. S., Wong, E. L., & Che, C. M. (2008). 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. Chemistry (Weinheim an Der Bergstrasse, Germany), 14(18), 5495-506. https://doi.org/10.1002/chem.200701563
Tong GS, Wong EL, Che CM. 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. Chemistry. 2008;14(18):5495-506. PubMed PMID: 18478515.
* Article titles in AMA citation format should be in sentence-case
TY - JOUR T1 - 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. AU - Tong,Glenna So Ming, AU - Wong,Ella Lai-Ming, AU - Che,Chi-Ming, PY - 2008/5/15/pubmed PY - 2008/8/16/medline PY - 2008/5/15/entrez SP - 5495 EP - 506 JF - Chemistry (Weinheim an der Bergstrasse, Germany) JO - Chemistry VL - 14 IS - 18 N2 - Density functional theory (DFT) calculations on trans-dioxo metal complexes containing saturated amine ligands, trans-[M(O)2(NH3)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 lambda approximately 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 pi(Fe-O)-->pi*(Fe-O) transition with B3LYP, in which pi and pi* are the bonding and antibonding combinations between the dpi(Fe) and ppi(O(2-)) orbitals. The FeVI/V reduction potential of trans-[Fe(O)2(NH3)2NMeH2)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''''-quinquepyridine; 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. SN - 0947-6539 UR - https://www.unboundmedicine.com/medline/citation/18478515/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_ L2 - https://doi.org/10.1002/chem.200701563 DB - PRIME DP - Unbound Medicine ER -