FRINK Linked Data Fragments server

Matches in SemOpenAlex for { <https://semopenalex.org/work/W2941512264> ?p ?o ?g. }

• W2941512264 endingPage "7485" @default.
• W2941512264 startingPage "7473" @default.
• W2941512264 abstract "A growing and useful class of alkene coupling reactions involve hydrogen atom transfer (HAT) from a metal-hydride species to an alkene to form a free radical, which is responsible for subsequent bond formation. Here, we use a combination of experimental and computational investigations to map out the mechanistic details of iron-catalyzed reductive alkene cross-coupling, an important representative of the HAT alkene reactions. We are able to explain several observations that were previously mysterious. First, the rate-limiting step in the catalytic cycle is the formation of the reactive Fe–H intermediate, elucidating the importance of the choice of reductant. Second, the success of the catalytic system is attributable to the exceptionally weak (17 kcal/mol) Fe–H bond, which performs irreversible HAT to alkenes in contrast to previous studies on isolable hydride complexes where this addition was reversible. Third, the organic radical intermediates can reversibly form organometallic species, which helps to protect the free radicals from side reactions. Fourth, the previously accepted quenching of the postcoupling radical through stepwise electron transfer/proton transfer is not as favorable as alternative mechanisms. We find that there are two feasible pathways. One uses concerted proton-coupled electron transfer (PCET) from an iron(II) ethanol complex, which is facilitated because the O–H bond dissociation free energy is lowered by 30 kcal/mol upon metal binding. In an alternative pathway, an O-bound enolate-iron(III) complex undergoes proton shuttling from an iron-bound alcohol. These kinetic, spectroscopic, and computational studies identify key organometallic species and PCET steps that control selectivity and reactivity in metal-catalyzed HAT alkene coupling, and create a firm basis for elucidation of mechanisms in the growing class of HAT alkene cross-coupling reactions." @default.
• W2941512264 created "2019-05-03" @default.
• W2941512264 creator A5010430402 @default.
• W2941512264 creator A5024651579 @default.
• W2941512264 creator A5029597992 @default.
• W2941512264 creator A5038732109 @default.
• W2941512264 creator A5073644685 @default.
• W2941512264 date "2019-04-26" @default.
• W2941512264 modified "2023-10-14" @default.
• W2941512264 title "Roles of Iron Complexes in Catalytic Radical Alkene Cross-Coupling: A Computational and Mechanistic Study" @default.
• W2941512264 cites W1179847255 @default.
• W2941512264 cites W1516536514 @default.
• W2941512264 cites W1703406098 @default.
• W2941512264 cites W188841472 @default.
• W2941512264 cites W1889384145 @default.
• W2941512264 cites W1964352868 @default.
• W2941512264 cites W1971309921 @default.
• W2941512264 cites W1972040015 @default.
• W2941512264 cites W1976643343 @default.
• W2941512264 cites W1976821096 @default.
• W2941512264 cites W197782333 @default.
• W2941512264 cites W1979259658 @default.
• W2941512264 cites W1985222948 @default.
• W2941512264 cites W1986269250 @default.
• W2941512264 cites W1986574135 @default.
• W2941512264 cites W1989325303 @default.
• W2941512264 cites W1991451780 @default.
• W2941512264 cites W1995000974 @default.
• W2941512264 cites W2001786664 @default.
• W2941512264 cites W2009911625 @default.
• W2941512264 cites W2010811684 @default.
• W2941512264 cites W2013757557 @default.
• W2941512264 cites W2014059469 @default.
• W2941512264 cites W2014935637 @default.
• W2941512264 cites W2022033362 @default.
• W2941512264 cites W2025858162 @default.
• W2941512264 cites W2029268569 @default.
• W2941512264 cites W2030435065 @default.
• W2941512264 cites W2032421968 @default.
• W2941512264 cites W2033116763 @default.
• W2941512264 cites W2036303486 @default.
• W2941512264 cites W2037424279 @default.
• W2941512264 cites W2037431388 @default.
• W2941512264 cites W2038860808 @default.
• W2941512264 cites W2041930594 @default.
• W2941512264 cites W2042710196 @default.
• W2941512264 cites W2043244040 @default.
• W2941512264 cites W2044733923 @default.
• W2941512264 cites W2046798561 @default.
• W2941512264 cites W2047470444 @default.
• W2941512264 cites W2049186688 @default.
• W2941512264 cites W2051836579 @default.
• W2941512264 cites W2051997051 @default.
• W2941512264 cites W2054178986 @default.
• W2941512264 cites W2055032779 @default.
• W2941512264 cites W2061682742 @default.
• W2941512264 cites W2079068427 @default.
• W2941512264 cites W2081104557 @default.
• W2941512264 cites W2081656971 @default.
• W2941512264 cites W2083469618 @default.
• W2941512264 cites W2085155714 @default.
• W2941512264 cites W2089541261 @default.
• W2941512264 cites W2095439324 @default.
• W2941512264 cites W2111311564 @default.
• W2941512264 cites W2112304777 @default.
• W2941512264 cites W2113803424 @default.
• W2941512264 cites W2114651412 @default.
• W2941512264 cites W2121408071 @default.
• W2941512264 cites W2124129640 @default.
• W2941512264 cites W2126111554 @default.
• W2941512264 cites W2127973708 @default.
• W2941512264 cites W2144978325 @default.
• W2941512264 cites W2166221263 @default.
• W2941512264 cites W2278208046 @default.
• W2941512264 cites W2286108466 @default.
• W2941512264 cites W2293392862 @default.
• W2941512264 cites W2310319538 @default.
• W2941512264 cites W2314073443 @default.
• W2941512264 cites W2318510297 @default.
• W2941512264 cites W2321459754 @default.
• W2941512264 cites W2324835515 @default.
• W2941512264 cites W2326289441 @default.
• W2941512264 cites W2331314274 @default.
• W2941512264 cites W2333471195 @default.
• W2941512264 cites W2335850755 @default.
• W2941512264 cites W2402718701 @default.
• W2941512264 cites W2413801142 @default.
• W2941512264 cites W2462600521 @default.
• W2941512264 cites W2465160305 @default.
• W2941512264 cites W2469190439 @default.
• W2941512264 cites W2469507214 @default.
• W2941512264 cites W2479201755 @default.
• W2941512264 cites W2488628364 @default.
• W2941512264 cites W2489170855 @default.
• W2941512264 cites W2504026546 @default.
• W2941512264 cites W2507764024 @default.
• W2941512264 cites W2519369283 @default.
• W2941512264 cites W2520813356 @default.

• next