FRINK Linked Data Fragments server

Matches in SemOpenAlex for { <https://semopenalex.org/work/W2010816113> ?p ?o ?g. }

• W2010816113 endingPage "17104" @default.
• W2010816113 startingPage "17090" @default.
• W2010816113 abstract "We describe herein the hydrogen-atom transfer (HAT)/proton-coupled electron-transfer (PCET) reactivity for Fe(IV)-oxo and Fe(III)-oxo complexes (1-4) that activate C-H, N-H, and O-H bonds in 9,10-dihydroanthracene (S1), dimethylformamide (S2), 1,2-diphenylhydrazine (S3), p-methoxyphenol (S4), and 1,4-cyclohexadiene (S5). In 1-3, the iron is pentacoordinated by tris[N'-tert-butylureaylato)-N-ethylene]aminato ([H3buea](3-)) or its derivatives. These complexes are basic, in the order 3 ≫ 1 > 2. Oxidant 4, [Fe(IV)N4Py(O)](2+) (N4Py: N,N-bis(2-pyridylmethyl)bis(2-pyridyl)methylamine), is the least basic oxidant. The DFT results match experimental trends and exhibit a mechanistic spectrum ranging from concerted HAT and PCET reactions to concerted-asynchronous proton transfer (PT)/electron transfer (ET) mechanisms, all the way to PT. The singly occupied orbital along the O···H···X (X = C, N, O) moiety in the TS shows clearly that in the PCET cases, the electron is transferred separately from the proton. The Bell-Evans-Polanyi principle does not account for the observed reactivity pattern, as evidenced by the scatter in the plot of calculated barrier vs reactions driving forces. However, a plot of the deformation energy in the TS vs the respective barrier provides a clear signature of the HAT/PCET dichotomy. Thus, in all C-H bond activations, the barrier derives from the deformation energy required to create the TS, whereas in N-H/O-H bond activations, the deformation energy is much larger than the corresponding barrier, indicating the presence of a stabilizing interaction between the TS fragments. A valence bond model is used to link the observed results with the basicity/acidity of the reactants." @default.
• W2010816113 created "2016-06-24" @default.
• W2010816113 creator A5012680779 @default.
• W2010816113 creator A5026786226 @default.
• W2010816113 creator A5042697647 @default.
• W2010816113 creator A5043751476 @default.
• W2010816113 date "2013-11-04" @default.
• W2010816113 modified "2023-10-18" @default.
• W2010816113 title "Dichotomous Hydrogen Atom Transfer vs Proton-Coupled Electron Transfer During Activation of X–H Bonds (X = C, N, O) by Nonheme Iron–Oxo Complexes of Variable Basicity" @default.
• W2010816113 cites W1087938070 @default.
• W2010816113 cites W1964596038 @default.
• W2010816113 cites W1966182479 @default.
• W2010816113 cites W1966217622 @default.
• W2010816113 cites W1966792574 @default.
• W2010816113 cites W1967161172 @default.
• W2010816113 cites W1967700647 @default.
• W2010816113 cites W1968400590 @default.
• W2010816113 cites W1969026406 @default.
• W2010816113 cites W1970152976 @default.
• W2010816113 cites W1970549136 @default.
• W2010816113 cites W1970900112 @default.
• W2010816113 cites W1970915662 @default.
• W2010816113 cites W1972040015 @default.
• W2010816113 cites W1972288310 @default.
• W2010816113 cites W1973427525 @default.
• W2010816113 cites W1974892037 @default.
• W2010816113 cites W1975262546 @default.
• W2010816113 cites W1976205221 @default.
• W2010816113 cites W1978038032 @default.
• W2010816113 cites W1978536813 @default.
• W2010816113 cites W1978607450 @default.
• W2010816113 cites W1981368803 @default.
• W2010816113 cites W1981451973 @default.
• W2010816113 cites W1985769118 @default.
• W2010816113 cites W1986531390 @default.
• W2010816113 cites W1988091937 @default.
• W2010816113 cites W1991875011 @default.
• W2010816113 cites W1993895867 @default.
• W2010816113 cites W1995825925 @default.
• W2010816113 cites W1996403326 @default.
• W2010816113 cites W1997785740 @default.
• W2010816113 cites W1997823913 @default.
• W2010816113 cites W1998817017 @default.
• W2010816113 cites W1999582957 @default.
• W2010816113 cites W1999760359 @default.
• W2010816113 cites W2002384424 @default.
• W2010816113 cites W2006361938 @default.
• W2010816113 cites W2006642056 @default.
• W2010816113 cites W2007933544 @default.
• W2010816113 cites W2007986320 @default.
• W2010816113 cites W2008423326 @default.
• W2010816113 cites W2011215428 @default.
• W2010816113 cites W2011890891 @default.
• W2010816113 cites W2011905130 @default.
• W2010816113 cites W2012172107 @default.
• W2010816113 cites W2015387651 @default.
• W2010816113 cites W2015661213 @default.
• W2010816113 cites W2019337791 @default.
• W2010816113 cites W2019692171 @default.
• W2010816113 cites W2023271753 @default.
• W2010816113 cites W2025161609 @default.
• W2010816113 cites W2027174785 @default.
• W2010816113 cites W2028281685 @default.
• W2010816113 cites W2030795020 @default.
• W2010816113 cites W2032753263 @default.
• W2010816113 cites W2032849703 @default.
• W2010816113 cites W2035419439 @default.
• W2010816113 cites W2038568113 @default.
• W2010816113 cites W2040527989 @default.
• W2010816113 cites W2041930594 @default.
• W2010816113 cites W2041947293 @default.
• W2010816113 cites W2045836463 @default.
• W2010816113 cites W2046657548 @default.
• W2010816113 cites W2051649868 @default.
• W2010816113 cites W2056768042 @default.
• W2010816113 cites W2057331738 @default.
• W2010816113 cites W2060696113 @default.
• W2010816113 cites W2060738076 @default.
• W2010816113 cites W2062244899 @default.
• W2010816113 cites W2063512690 @default.
• W2010816113 cites W2064325695 @default.
• W2010816113 cites W2064517416 @default.
• W2010816113 cites W2065519066 @default.
• W2010816113 cites W2066311520 @default.
• W2010816113 cites W2068185427 @default.
• W2010816113 cites W2068358349 @default.
• W2010816113 cites W2068375215 @default.
• W2010816113 cites W2071766178 @default.
• W2010816113 cites W2073637781 @default.
• W2010816113 cites W2077307846 @default.
• W2010816113 cites W2078899588 @default.
• W2010816113 cites W2081012283 @default.
• W2010816113 cites W2082037815 @default.
• W2010816113 cites W2084460084 @default.
• W2010816113 cites W2085831526 @default.
• W2010816113 cites W2089275038 @default.
• W2010816113 cites W2090027364 @default.
• W2010816113 cites W2092157292 @default.

• next