Matches in SemOpenAlex for { <https://semopenalex.org/work/W1154019702> ?p ?o ?g. }
- W1154019702 endingPage "170" @default.
- W1154019702 startingPage "165" @default.
- W1154019702 abstract "Density functional theory (DFT) calculations were used to study the mechanisms for hydrogenation of biomass-derived levulinic acid (LA) to γ-valerolactone (GVL) catalyzed by PNP-ligated (PNP = 2,6-bis(di-ter-butylphosphinomethyl) pyridine) iridium complexes, (tBuPNP)IrH3, 1. The transformation proceeds dearomatization/rearomatization including four stages: hydride transfer to give LA-H− and dihydride iridium specie (BtuPNP)IrH2+, methylene proton in the PNP ligand transfer to substrate to form γ-hydroxyvaleric acid (HVA), catalyst regeneration via H2 splitting, cyclization of HVA to GVL. Compared with the hydrogenation of CO2 catalyzed by the same complex, herein the rate-limiting step is the hydride transfer step rather than the methylene proton transfer. The calculations show that the hydride transfer step has a significantly higher barrier (21.1 vs 5.3 kcal mol−1 for the hydrogenation of CO2). Besides, the cyclization is very easily achieved due to the low barrier. As an alternative pathway, different from the above dearomatization/rearomatization process, a base abstracts a proton from the dihydrogen ligand to form the trihydride iridium with a free energy barrier of 24.6 kcal mol−1. Our results will help in the understanding of the mechanisms of hydrogenation of LA to GVL catalyzed by metal complexes." @default.
- W1154019702 created "2016-06-24" @default.
- W1154019702 creator A5023639462 @default.
- W1154019702 creator A5038199259 @default.
- W1154019702 date "2015-11-01" @default.
- W1154019702 modified "2023-10-16" @default.
- W1154019702 title "Hydrogenation of biomass-derived levulinic acid to γ-valerolactone catalyzed by PNP-Ir pincer complexes: A computational study" @default.
- W1154019702 cites W1965825136 @default.
- W1154019702 cites W1968066573 @default.
- W1154019702 cites W1975506590 @default.
- W1154019702 cites W1975904524 @default.
- W1154019702 cites W1977902200 @default.
- W1154019702 cites W1979675865 @default.
- W1154019702 cites W1983566725 @default.
- W1154019702 cites W1987643155 @default.
- W1154019702 cites W1992030014 @default.
- W1154019702 cites W1995279701 @default.
- W1154019702 cites W1998321859 @default.
- W1154019702 cites W2005213632 @default.
- W1154019702 cites W2008852069 @default.
- W1154019702 cites W2011215428 @default.
- W1154019702 cites W2013474390 @default.
- W1154019702 cites W2014767176 @default.
- W1154019702 cites W2015723183 @default.
- W1154019702 cites W2021231925 @default.
- W1154019702 cites W2027310080 @default.
- W1154019702 cites W2028632252 @default.
- W1154019702 cites W2038935041 @default.
- W1154019702 cites W2050158761 @default.
- W1154019702 cites W2052808022 @default.
- W1154019702 cites W2054976385 @default.
- W1154019702 cites W2055450639 @default.
- W1154019702 cites W2065668060 @default.
- W1154019702 cites W2075087451 @default.
- W1154019702 cites W2078527804 @default.
- W1154019702 cites W2079458939 @default.
- W1154019702 cites W2085336624 @default.
- W1154019702 cites W2087081982 @default.
- W1154019702 cites W2091554172 @default.
- W1154019702 cites W2093403227 @default.
- W1154019702 cites W2102318977 @default.
- W1154019702 cites W2103098018 @default.
- W1154019702 cites W2104119823 @default.
- W1154019702 cites W2105081527 @default.
- W1154019702 cites W2110659651 @default.
- W1154019702 cites W2122034226 @default.
- W1154019702 cites W2122160329 @default.
- W1154019702 cites W2123645090 @default.
- W1154019702 cites W2125845584 @default.
- W1154019702 cites W2126452174 @default.
- W1154019702 cites W2127350857 @default.
- W1154019702 cites W2142527379 @default.
- W1154019702 cites W2143958801 @default.
- W1154019702 cites W2145110720 @default.
- W1154019702 cites W2151760902 @default.
- W1154019702 cites W2161950784 @default.
- W1154019702 cites W2166925424 @default.
- W1154019702 cites W2313950432 @default.
- W1154019702 cites W2317059881 @default.
- W1154019702 cites W2320578457 @default.
- W1154019702 cites W2324462072 @default.
- W1154019702 cites W2326580187 @default.
- W1154019702 cites W2327124060 @default.
- W1154019702 cites W2327440444 @default.
- W1154019702 cites W2331489872 @default.
- W1154019702 cites W2362690370 @default.
- W1154019702 cites W3105642836 @default.
- W1154019702 doi "https://doi.org/10.1016/j.jorganchem.2015.08.020" @default.
- W1154019702 hasPublicationYear "2015" @default.
- W1154019702 type Work @default.
- W1154019702 sameAs 1154019702 @default.
- W1154019702 citedByCount "13" @default.
- W1154019702 countsByYear W11540197022016 @default.
- W1154019702 countsByYear W11540197022017 @default.
- W1154019702 countsByYear W11540197022018 @default.
- W1154019702 countsByYear W11540197022019 @default.
- W1154019702 countsByYear W11540197022020 @default.
- W1154019702 countsByYear W11540197022021 @default.
- W1154019702 countsByYear W11540197022022 @default.
- W1154019702 crossrefType "journal-article" @default.
- W1154019702 hasAuthorship W1154019702A5023639462 @default.
- W1154019702 hasAuthorship W1154019702A5038199259 @default.
- W1154019702 hasConcept C116569031 @default.
- W1154019702 hasConcept C155647269 @default.
- W1154019702 hasConcept C161790260 @default.
- W1154019702 hasConcept C170493617 @default.
- W1154019702 hasConcept C178790620 @default.
- W1154019702 hasConcept C185592680 @default.
- W1154019702 hasConcept C2776715866 @default.
- W1154019702 hasConcept C2777454769 @default.
- W1154019702 hasConcept C2777961443 @default.
- W1154019702 hasConcept C2778468751 @default.
- W1154019702 hasConcept C2779485729 @default.
- W1154019702 hasConcept C2780604391 @default.
- W1154019702 hasConcept C512968161 @default.
- W1154019702 hasConcept C528581852 @default.
- W1154019702 hasConcept C55493867 @default.
- W1154019702 hasConcept C555196967 @default.