Matches in SemOpenAlex for { <https://semopenalex.org/work/W2070884404> ?p ?o ?g. }
- W2070884404 endingPage "7042" @default.
- W2070884404 startingPage "7034" @default.
- W2070884404 abstract "The [Ni(PR2NR′2)2]2+ complexes (where PR2NR′2 is 1,5-R′-3,7-R-1,5-diaza-3,7-diphosphacyclooctane) are fast electrocatalysts for H2 production and oxidation. Binding of a fifth ligand (CH3CN or BF4–) or chair/boat isomerization has the potential to slow catalysis by blocking the addition of H2 or by incorrectly positioning the pendant amines. We report the structural dynamics of a series of nickel complexes characterized by NMR spectroscopy and theoretical modeling to examine the effects of the fifth ligand for the Ni(II) complexes, including CH3CN, BF4–, Cl–, and H–, as well as the differences in dynamics between the Ni(II) and Ni(0) oxidation states. A fast exchange process was observed for the [Ni(CH3CN)(PR2NR′2)2]2+ complexes, with rates ranging from 104 to 107 s–1 depending on the phosphorus and nitrogen substituents on the PR2NR′2 ligand. This exchange process was identified to occur through a multistep mechanism, which consists of dissociation of the acetonitrile, boat/chair isomerization of each of the four rings (including nitrogen inversion), and reassociation of an acetonitrile on the opposite side of the complex. The rate of the chair/boat inversion was found to be influenced by varying the substituent on the nitrogen atom, but the rate of the overall exchange process is at least an order of magnitude faster than the catalytic rate in acetonitrile, demonstrating that the structural dynamics of the [Ni(CH3CN)(PR2NR′2)2]2+ complexes do not hinder catalysis. Possible catalytic implications of the coordination of a fifth ligand to the Ni(II) complex are discussed." @default.
- W2070884404 created "2016-06-24" @default.
- W2070884404 creator A5001426799 @default.
- W2070884404 creator A5006329563 @default.
- W2070884404 creator A5009857671 @default.
- W2070884404 creator A5022980951 @default.
- W2070884404 creator A5031987406 @default.
- W2070884404 creator A5034580690 @default.
- W2070884404 creator A5059588554 @default.
- W2070884404 creator A5078039482 @default.
- W2070884404 creator A5082146943 @default.
- W2070884404 creator A5086225713 @default.
- W2070884404 creator A5090105637 @default.
- W2070884404 date "2013-11-15" @default.
- W2070884404 modified "2023-09-27" @default.
- W2070884404 title "Conformational Dynamics and Proton Relay Positioning in Nickel Catalysts for Hydrogen Production and Oxidation" @default.
- W2070884404 cites W115304618 @default.
- W2070884404 cites W1972293646 @default.
- W2070884404 cites W1978538796 @default.
- W2070884404 cites W1981368803 @default.
- W2070884404 cites W1982671514 @default.
- W2070884404 cites W1983814181 @default.
- W2070884404 cites W1985684677 @default.
- W2070884404 cites W1987832365 @default.
- W2070884404 cites W1989060947 @default.
- W2070884404 cites W1991905037 @default.
- W2070884404 cites W2000770615 @default.
- W2070884404 cites W2004837355 @default.
- W2070884404 cites W2014166972 @default.
- W2070884404 cites W2015723183 @default.
- W2070884404 cites W2023698367 @default.
- W2070884404 cites W2030489166 @default.
- W2070884404 cites W2030687437 @default.
- W2070884404 cites W2030841140 @default.
- W2070884404 cites W2034258001 @default.
- W2070884404 cites W2037756241 @default.
- W2070884404 cites W2038199329 @default.
- W2070884404 cites W2038968494 @default.
- W2070884404 cites W2039559098 @default.
- W2070884404 cites W2044591029 @default.
- W2070884404 cites W2046877435 @default.
- W2070884404 cites W2054406704 @default.
- W2070884404 cites W2054704030 @default.
- W2070884404 cites W2055905047 @default.
- W2070884404 cites W2057137567 @default.
- W2070884404 cites W2057830422 @default.
- W2070884404 cites W2058848030 @default.
- W2070884404 cites W2062220773 @default.
- W2070884404 cites W2065818181 @default.
- W2070884404 cites W2066951434 @default.
- W2070884404 cites W2067011309 @default.
- W2070884404 cites W2070565454 @default.
- W2070884404 cites W2072796268 @default.
- W2070884404 cites W2081693079 @default.
- W2070884404 cites W2086634221 @default.
- W2070884404 cites W2089799306 @default.
- W2070884404 cites W2095949414 @default.
- W2070884404 cites W2116255848 @default.
- W2070884404 cites W2143981217 @default.
- W2070884404 cites W2149655632 @default.
- W2070884404 doi "https://doi.org/10.1021/om400695w" @default.
- W2070884404 hasPublicationYear "2013" @default.
- W2070884404 type Work @default.
- W2070884404 sameAs 2070884404 @default.
- W2070884404 citedByCount "34" @default.
- W2070884404 countsByYear W20708844042014 @default.
- W2070884404 countsByYear W20708844042015 @default.
- W2070884404 countsByYear W20708844042016 @default.
- W2070884404 countsByYear W20708844042017 @default.
- W2070884404 countsByYear W20708844042018 @default.
- W2070884404 countsByYear W20708844042019 @default.
- W2070884404 countsByYear W20708844042021 @default.
- W2070884404 countsByYear W20708844042022 @default.
- W2070884404 countsByYear W20708844042023 @default.
- W2070884404 crossrefType "journal-article" @default.
- W2070884404 hasAuthorship W2070884404A5001426799 @default.
- W2070884404 hasAuthorship W2070884404A5006329563 @default.
- W2070884404 hasAuthorship W2070884404A5009857671 @default.
- W2070884404 hasAuthorship W2070884404A5022980951 @default.
- W2070884404 hasAuthorship W2070884404A5031987406 @default.
- W2070884404 hasAuthorship W2070884404A5034580690 @default.
- W2070884404 hasAuthorship W2070884404A5059588554 @default.
- W2070884404 hasAuthorship W2070884404A5078039482 @default.
- W2070884404 hasAuthorship W2070884404A5082146943 @default.
- W2070884404 hasAuthorship W2070884404A5086225713 @default.
- W2070884404 hasAuthorship W2070884404A5090105637 @default.
- W2070884404 hasConcept C102931765 @default.
- W2070884404 hasConcept C116569031 @default.
- W2070884404 hasConcept C126661725 @default.
- W2070884404 hasConcept C147789679 @default.
- W2070884404 hasConcept C155647269 @default.
- W2070884404 hasConcept C161790260 @default.
- W2070884404 hasConcept C170493617 @default.
- W2070884404 hasConcept C178790620 @default.
- W2070884404 hasConcept C185592680 @default.
- W2070884404 hasConcept C2777463227 @default.
- W2070884404 hasConcept C2778689049 @default.
- W2070884404 hasConcept C504270822 @default.