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Structural Characte...
Structural Characterization of a Series of N5-Ligated MnIV-Oxo Species
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- Massie, Allyssa A. (författare)
- University of Kansas Lawrence
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- Denler, Melissa C. (författare)
- University of Kansas Lawrence
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- Singh, Reena (författare)
- Lund University,Lunds universitet,Kemisk fysik,Enheten för fysikalisk och teoretisk kemi,Kemiska institutionen,Institutioner vid LTH,Lunds Tekniska Högskola,Chemical Physics,Physical and theoretical chemistry,Department of Chemistry,Departments at LTH,Faculty of Engineering, LTH
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- Sinha, Arup (författare)
- Lund University,Lunds universitet,Kemisk fysik,Enheten för fysikalisk och teoretisk kemi,Kemiska institutionen,Institutioner vid LTH,Lunds Tekniska Högskola,Chemical Physics,Physical and theoretical chemistry,Department of Chemistry,Departments at LTH,Faculty of Engineering, LTH,Vellore Institute of Technology University
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- Nordlander, Ebbe (författare)
- Lund University,Lunds universitet,Kemisk fysik,Enheten för fysikalisk och teoretisk kemi,Kemiska institutionen,Institutioner vid LTH,Lunds Tekniska Högskola,Chemical Physics,Physical and theoretical chemistry,Department of Chemistry,Departments at LTH,Faculty of Engineering, LTH
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- Jackson, Timothy A. (författare)
- University of Kansas Lawrence
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(creator_code:org_t)
- 2019-12-20
- 2020
- Engelska 13 s.
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Ingår i: Chemistry - A European Journal. - : Wiley. - 0947-6539 .- 1521-3765. ; 26:4, s. 900-912
- Relaterad länk:
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Abstract
Ämnesord
Stäng
- Analysis of extended X-ray absorption fine structure (EXAFS) data for the MnIV-oxo complexes [MnIV(O)(DMMN4py)]2+, [MnIV(O)(2pyN2B)]2+, and [MnIV(O)(2pyN2Q)]2+ (DMMN4py=N,N-bis(4-methoxy-3,5-dimethyl-2-pyridylmethyl)-N-bis(2-pyridyl)methylamine; 2pyN2B=(N-bis(1-methyl-2-benzimidazolyl)methyl-N-(bis-2-pyridylmethyl)amine, and 2pyN2Q=N,N-bis(2-pyridyl)-N,N-bis(2-quinolylmethyl)methanamine) afforded Mn=O and Mn−N bond lengths. The Mn=O distances for [MnIV(O)(DMMN4py)]2+ and [MnIV(O)(2pyN2B)]2+ are 1.72 and 1.70 Å, respectively. In contrast, the Mn=O distance for [MnIV(O)(2pyN2Q)]2+ was significantly longer (1.76 Å). We attribute this long distance to sample heterogeneity, which is reasonable given the reduced stability of [MnIV(O)(2pyN2Q)]2+. The Mn=O distances for [MnIV(O)(DMMN4py)]2+ and [MnIV(O)(2pyN2B)]2+ could only be well-reproduced using DFT-derived models that included strong hydrogen-bonds between second-sphere solvent 2,2,2-trifluoroethanol molecules and the oxo ligand. These results suggest an important role for the 2,2,2-trifluoroethanol solvent in stabilizing MnIV-oxo adducts. The DFT methods were extended to investigate the structure of the putative [MnIV(O)(N4py)]2+⋅(HOTf)2 adduct. These computations suggest that a MnIV-hydroxo species is most consistent with the available experimental data.
Ämnesord
- NATURVETENSKAP -- Kemi -- Teoretisk kemi (hsv//swe)
- NATURAL SCIENCES -- Chemical Sciences -- Theoretical Chemistry (hsv//eng)
Nyckelord
- DFT calculations
- electronic structure
- oxido ligands
- spectroscopy
- X-ray absorption spectroscopy
Publikations- och innehållstyp
- art (ämneskategori)
- ref (ämneskategori)
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