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Enhanced Understand...
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Singh, PriyaUniversity of Kansas Lawrence
(författare)
Enhanced Understanding of Structure-Function Relationships for Oxomanganese(IV) Complexes
- Artikel/kapitelEngelska2023
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Nummerbeteckningar
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LIBRIS-ID:oai:lup.lub.lu.se:cf560361-f1da-431e-994d-4f15c6624501
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https://lup.lub.lu.se/record/cf560361-f1da-431e-994d-4f15c6624501URI
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https://doi.org/10.1021/acs.inorgchem.3c00600DOI
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Språk:engelska
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Sammanfattning på:engelska
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Ämneskategori:art swepub-publicationtype
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Ämneskategori:ref swepub-contenttype
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A series of manganese(II) and oxomanganese(IV) complexes supported by neutral, pentadentate ligands with varied equatorial ligand-field strength (N3pyQ, N2py2I, and N4pyMe2) were synthesized and then characterized using structural and spectroscopic methods. On the basis of electronic absorption spectroscopy, the [MnIV(O)(N4pyMe2)]2+ complex has the weakest equatorial ligand field among a set of similar MnIV-oxo species. In contrast, [MnIV(O)(N2py2I)]2+ shows the strongest equatorial ligand-field strength for this same series. We examined the influence of these changes in electronic structure on the reactivity of the oxomanganese(IV) complexes using hydrocarbons and thioanisole as substrates. The [MnIV(O)(N3pyQ)]2+ complex, which contains one quinoline and three pyridine donors in the equatorial plane, ranks among the fastest MnIV-oxo complexes in C-H bond and thioanisole oxidation. While a weak equatorial ligand field has been associated with high reactivity, the [MnIV(O)(N4pyMe2)]2+ complex is only a modest oxidant. Buried volume plots suggest that steric factors dampen the reactivity of this complex. Trends in reactivity were examined using density functional theory (DFT)-computed bond dissociation free energies (BDFEs) of the MnIIIO-H and MnIV ≡ O bonds. We observe an excellent correlation between MnIV≡O BDFEs and rates of thioanisole oxidation, but more scatter is observed between hydrocarbon oxidation rates and the MnIIIO-H BDFEs.
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Biuppslag (personer, institutioner, konferenser, titlar ...)
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Lee, YuriUniversity of Kansas Lawrence
(författare)
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Mayfield, Jaycee R.University of Kansas Lawrence
(författare)
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Singh, ReenaLund 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(Swepub:lu)chem-res
(författare)
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Denler, Melissa C.University of Kansas Lawrence
(författare)
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Jones, Shannon D.University of Kansas Lawrence
(författare)
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Day, Victor W.University of Kansas Lawrence
(författare)
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Nordlander, EbbeLund University,Lunds universitet,Kemisk fysik,Enheten för fysikalisk och teoretisk kemi,Kemiska institutionen,Institutioner vid LTH,Lunds Tekniska Högskola,LU profilområde: Ljus och material,Lunds universitets profilområden,Chemical Physics,Physical and theoretical chemistry,Department of Chemistry,Departments at LTH,Faculty of Engineering, LTH,LU Profile Area: Light and Materials,Lund University Profile areas(Swepub:lu)ook1-eno
(författare)
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Jackson, Timothy A.University of Kansas Lawrence
(författare)
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University of Kansas LawrenceKemisk fysik
(creator_code:org_t)
Sammanhörande titlar
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Ingår i:Inorganic Chemistry62:45, s. 18357-183740020-1669
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