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Reversible PCET and...
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Elinburg, Jessica K.Boston University
(författare)
Reversible PCET and Ambient Catalytic Oxidative Alcohol Dehydrogenation by {V=O} Perfluoropinacolate Complexes
- Artikel/kapitelEngelska2020
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2020-10-29
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American Chemical Society (ACS),2020
Nummerbeteckningar
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LIBRIS-ID:oai:lup.lub.lu.se:4d3c126f-ad92-4410-8583-2d2edd61817d
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https://lup.lub.lu.se/record/4d3c126f-ad92-4410-8583-2d2edd61817dURI
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https://doi.org/10.1021/acs.inorgchem.0c02367DOI
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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
Anmärkningar
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A new air-stable catalyst for the oxidative dehydrogenation of benzylic alcohols under ambient conditions has been developed. The synthesis and characterization of this compound and the related monomeric and dimeric V(IV)- and V(V)-pinF (pinF = perfluoropinacolate) complexes are reported herein. Monomeric V(IV) complex (Me4N)2[V(O)(pinF)2] (1) and dimeric (μ-O)2-bridged V(V) complex (Me4N)2[V2(O)2(μ-O)2(pinF)2] (3a) are prepared in water under ambient conditions. Monomeric V(V) complex (Me4N)[V(O)(pinF)2] (2) may be generated via chemical oxidation of 1 under an inert atmosphere, but dimerizes to 3a upon exposure to air. Complexes 1 and 2 display a perfectly reversible VIV/V couple at 20 mV (vs Ag/AgNO3), whereas a quasi-reversible VIV/V couple at -865 mV is found for 3a. Stoichiometric reactions of 3a with both fluorenol and TEMPOH result in the formation of (Me4N)2[V2(O)2(μ-OH)2(pinF)2] (4a), which contains two V(IV) centers that display antiferromagnetic coupling. In order to structurally characterize the dinuclear anion of 4a, {K(18C6)}+ countercations were employed, which formed stabilizing K···O interactions between the counterion and each terminal oxo moiety and H-bonding between the oxygen atoms of the crown ether and μ-OH bridges of the dimer, resulting in {K(18C6)}2[V2(O)2(μ-OH)2(pinF)2] (4b). The formal storage of H2 in 4a is reversible and proton-coupled electron transfer (PCET) from crystals of 4a regenerates 3a upon exposure to air over the course of several days. Furthermore, the reaction of 3a (2%) under ambient conditions with excess fluorenol, cinnamyl alcohol, or benzyl alcohol resulted in the selective formation of fluorenone (82% conversion), cinnamaldehyde (40%), or benzaldehyde (7%), respectively, reproducing oxidative alcohol dehydrogenation (OAD) chemistry known for VOx surfaces and demonstrating, in air, the thermodynamically challenging selective oxidation of alcohols to aldehydes/ketones.
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Biuppslag (personer, institutioner, konferenser, titlar ...)
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Carter, Samantha L.Boston University
(författare)
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Nelson, Joshua J.M.Boston University
(författare)
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Fraser, Douglas G.Boston University
(författare)
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Crockett, Michael P.Boston College
(författare)
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Beeler, Aaron B.Boston University
(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,Chemical Physics,Physical and theoretical chemistry,Department of Chemistry,Departments at LTH,Faculty of Engineering, LTH(Swepub:lu)ook1-eno
(författare)
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Rheingold, Arnold L.University of California, San Diego
(författare)
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Doerrer, Linda H.Boston University
(författare)
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Boston UniversityBoston College
(creator_code:org_t)
Sammanhörande titlar
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Ingår i:Inorganic Chemistry: American Chemical Society (ACS)59:22, s. 16500-165130020-16691520-510X
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