Matches in SemOpenAlex for { <https://semopenalex.org/work/W3095802273> ?p ?o ?g. }
- W3095802273 endingPage "2064" @default.
- W3095802273 startingPage "2050" @default.
- W3095802273 abstract "Abstract The degradation pathways of highly active [Cp*Ir(κ 2 ‐ N , N ‐R‐pica)Cl] catalysts (pica=picolinamidate; 1 R=H, 2 R=Me) for formic acid (FA) dehydrogenation were investigated by NMR spectroscopy and DFT calculations. Under acidic conditions (1 equiv. of HNO 3 ), 2 undergoes partial protonation of the amide moiety, inducing rapid κ 2 ‐ N , N to κ 2 ‐ N , O ligand isomerization. Consistently, DFT modeling on the simpler complex 1 showed that the κ 2 ‐ N , N key intermediate of FA dehydrogenation ( I NH ), bearing a N ‐protonated pica, can easily transform into the κ 2 ‐ N , O analogue ( I NH2 ; Δ G ≠ ≈11 kcal mol −1 , Δ G ≈−5 kcal mol −1 ). Intramolecular hydrogen liberation from I NH2 is predicted to be rather prohibitive (Δ G ≠ ≈26 kcal mol −1 , Δ G ≈23 kcal mol −1 ), indicating that FA dehydrogenation should involve mostly κ 2 ‐ N , N intermediates, at least at relatively high pH. Under FA dehydrogenation conditions, 2 was progressively consumed, and the vast majority of the Ir centers (58 %) were eventually found in the form of Cp*‐complexes with a pyridine‐amine ligand. This likely derived from hydrogenation of the pyridine‐carboxiamide via a hemiaminal intermediate, which could also be detected. Clear evidence for ligand hydrogenation being the main degradation pathway also for 1 was obtained, as further confirmed by spectroscopic and catalytic tests on the independently synthesized degradation product 1 c . DFT calculations confirmed that this side reaction is kinetically and thermodynamically accessible." @default.
- W3095802273 created "2020-11-09" @default.
- W3095802273 creator A5018816196 @default.
- W3095802273 creator A5028287179 @default.
- W3095802273 creator A5046771754 @default.
- W3095802273 creator A5052163219 @default.
- W3095802273 creator A5052592745 @default.
- W3095802273 creator A5062509948 @default.
- W3095802273 date "2020-12-23" @default.
- W3095802273 modified "2023-10-14" @default.
- W3095802273 title "Understanding the Deactivation Pathways of Iridium(III) Pyridine‐Carboxiamide Catalysts for Formic Acid Dehydrogenation" @default.
- W3095802273 cites W1536167388 @default.
- W3095802273 cites W1926108226 @default.
- W3095802273 cites W1973732695 @default.
- W3095802273 cites W1986829915 @default.
- W3095802273 cites W1995279701 @default.
- W3095802273 cites W2005692644 @default.
- W3095802273 cites W2013732865 @default.
- W3095802273 cites W2027436047 @default.
- W3095802273 cites W2027973394 @default.
- W3095802273 cites W2030687437 @default.
- W3095802273 cites W2055563809 @default.
- W3095802273 cites W2067769676 @default.
- W3095802273 cites W2070932605 @default.
- W3095802273 cites W2073328513 @default.
- W3095802273 cites W2084897153 @default.
- W3095802273 cites W2086957099 @default.
- W3095802273 cites W2093104167 @default.
- W3095802273 cites W2095825218 @default.
- W3095802273 cites W2096747776 @default.
- W3095802273 cites W2109977502 @default.
- W3095802273 cites W2116685481 @default.
- W3095802273 cites W2121556561 @default.
- W3095802273 cites W2122458806 @default.
- W3095802273 cites W2123612487 @default.
- W3095802273 cites W2126952850 @default.
- W3095802273 cites W2129993089 @default.
- W3095802273 cites W2135572322 @default.
- W3095802273 cites W2140156540 @default.
- W3095802273 cites W2142372587 @default.
- W3095802273 cites W2142527379 @default.
- W3095802273 cites W2147753670 @default.
- W3095802273 cites W2149570038 @default.
- W3095802273 cites W2150345533 @default.
- W3095802273 cites W2166198169 @default.
- W3095802273 cites W2167383445 @default.
- W3095802273 cites W2168873288 @default.
- W3095802273 cites W2170549062 @default.
- W3095802273 cites W2271627776 @default.
- W3095802273 cites W2290495632 @default.
- W3095802273 cites W2295137636 @default.
- W3095802273 cites W2296880544 @default.
- W3095802273 cites W2303569605 @default.
- W3095802273 cites W2340063144 @default.
- W3095802273 cites W2342502077 @default.
- W3095802273 cites W2511566604 @default.
- W3095802273 cites W2576674024 @default.
- W3095802273 cites W2620507452 @default.
- W3095802273 cites W2625631675 @default.
- W3095802273 cites W2745402964 @default.
- W3095802273 cites W2761959175 @default.
- W3095802273 cites W2763179737 @default.
- W3095802273 cites W2790435947 @default.
- W3095802273 cites W2792212637 @default.
- W3095802273 cites W2809111446 @default.
- W3095802273 cites W2891908446 @default.
- W3095802273 cites W2897943214 @default.
- W3095802273 cites W2938904872 @default.
- W3095802273 cites W2951688120 @default.
- W3095802273 cites W2964525466 @default.
- W3095802273 cites W3005067277 @default.
- W3095802273 cites W3007267427 @default.
- W3095802273 cites W3036723969 @default.
- W3095802273 cites W3038491089 @default.
- W3095802273 cites W4237177415 @default.
- W3095802273 cites W2001608433 @default.
- W3095802273 doi "https://doi.org/10.1002/chem.202003911" @default.
- W3095802273 hasPubMedId "https://pubmed.ncbi.nlm.nih.gov/33141938" @default.
- W3095802273 hasPublicationYear "2020" @default.
- W3095802273 type Work @default.
- W3095802273 sameAs 3095802273 @default.
- W3095802273 citedByCount "13" @default.
- W3095802273 countsByYear W30958022732021 @default.
- W3095802273 countsByYear W30958022732022 @default.
- W3095802273 countsByYear W30958022732023 @default.
- W3095802273 crossrefType "journal-article" @default.
- W3095802273 hasAuthorship W3095802273A5018816196 @default.
- W3095802273 hasAuthorship W3095802273A5028287179 @default.
- W3095802273 hasAuthorship W3095802273A5046771754 @default.
- W3095802273 hasAuthorship W3095802273A5052163219 @default.
- W3095802273 hasAuthorship W3095802273A5052592745 @default.
- W3095802273 hasAuthorship W3095802273A5062509948 @default.
- W3095802273 hasConcept C116569031 @default.
- W3095802273 hasConcept C119889771 @default.
- W3095802273 hasConcept C126661725 @default.
- W3095802273 hasConcept C145148216 @default.
- W3095802273 hasConcept C155647269 @default.
- W3095802273 hasConcept C161790260 @default.