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• W1996691955 endingPage "11241" @default.
• W1996691955 startingPage "11241" @default.
• W1996691955 abstract "The cationic iridium complex [Ir(OH2)2(phpy)2]+ (phpy = o-phenylpyridine) is among the most efficient mononuclear catalysts for water oxidation. The postulated active species is the oxo complex [Ir(O)(X)(phpy)2]n, with X = OH2 (n = +1), OH− (n = 0) or O2− (n = −1), depending on the pH. The reactivity of these species has been studied computationally at the DFT(B3LYP) level. The three [Ir(O)(X)(phpy)2]n complexes have an electrophilic Ir(V)-oxo moiety, which yields an O–O bond by undergoing a nucleophilic attack of water in the critical step of the mechanism. In this step, water transfers one proton to either the Ir(V)-oxo moiety or the ancillary X ligand. Five different reaction pathways associated with this acid/base mechanism have been characterized. The calculations show that the proton is preferably accepted by the X ligand, which plays a key role in the reaction. The higher the basicity of X, the lower the energy barrier associated with O–O bond formation. The anionic species, [Ir(O)2(phpy)2]−, which has the less electrophilic Ir(V)-oxo moiety but the most basic X ligand, promotes O–O bond formation through the lowest energy barrier, 14.5 kcal mol−1. The other two active species, [Ir(O)(OH)(phpy)2] and [Ir(O)(OH2)(phpy)2]+, which have more electrophilic Ir(V)-oxo moieties but less basic X ligands, involve higher energy barriers, 20.2 kcal mol−1 and 25.9 kcal mol−1, respectively. These results are in good agreement with experiments showing important pH effects in similar catalytic systems. The theoretical insight given by the present study can be useful in the design of more efficient water oxidation catalysts. The catalytic activity may increase by using ligand scaffolds bearing internal bases." @default.
• W1996691955 created "2016-06-24" @default.
• W1996691955 creator A5000266480 @default.
• W1996691955 creator A5036092302 @default.
• W1996691955 creator A5044914316 @default.
• W1996691955 creator A5078141702 @default.
• W1996691955 date "2011-01-01" @default.
• W1996691955 modified "2023-10-11" @default.
• W1996691955 title "Basic ancillary ligands promote O–O bond formation in iridium-catalyzed water oxidation: A DFT study" @default.
• W1996691955 cites W1087938070 @default.
• W1996691955 cites W1963597613 @default.
• W1996691955 cites W1964222547 @default.
• W1996691955 cites W1964570639 @default.
• W1996691955 cites W1964837435 @default.
• W1996691955 cites W1967045707 @default.
• W1996691955 cites W1969784611 @default.
• W1996691955 cites W1971275758 @default.
• W1996691955 cites W1972167384 @default.
• W1996691955 cites W1973721002 @default.
• W1996691955 cites W1973820731 @default.
• W1996691955 cites W1974475845 @default.
• W1996691955 cites W1974765083 @default.
• W1996691955 cites W1975492516 @default.
• W1996691955 cites W1975708211 @default.
• W1996691955 cites W1978438248 @default.
• W1996691955 cites W1979312227 @default.
• W1996691955 cites W1981768663 @default.
• W1996691955 cites W1982373014 @default.
• W1996691955 cites W1982685288 @default.
• W1996691955 cites W1984614201 @default.
• W1996691955 cites W1987275920 @default.
• W1996691955 cites W1989917955 @default.
• W1996691955 cites W2005777541 @default.
• W1996691955 cites W2005927404 @default.
• W1996691955 cites W2006151577 @default.
• W1996691955 cites W2007200392 @default.
• W1996691955 cites W2011715705 @default.
• W1996691955 cites W2012676584 @default.
• W1996691955 cites W2015723183 @default.
• W1996691955 cites W2017265384 @default.
• W1996691955 cites W2018016840 @default.
• W1996691955 cites W2018097469 @default.
• W1996691955 cites W2020973952 @default.
• W1996691955 cites W2022884415 @default.
• W1996691955 cites W2022977150 @default.
• W1996691955 cites W2023116072 @default.
• W1996691955 cites W2023271753 @default.
• W1996691955 cites W2023879527 @default.
• W1996691955 cites W2026673235 @default.
• W1996691955 cites W2030407485 @default.
• W1996691955 cites W2033033156 @default.
• W1996691955 cites W2038767330 @default.
• W1996691955 cites W2039475059 @default.
• W1996691955 cites W2042209259 @default.
• W1996691955 cites W2042339986 @default.
• W1996691955 cites W2043327592 @default.
• W1996691955 cites W2044469398 @default.
• W1996691955 cites W2046412723 @default.
• W1996691955 cites W2046488593 @default.
• W1996691955 cites W2047348553 @default.
• W1996691955 cites W2049638592 @default.
• W1996691955 cites W2054958899 @default.
• W1996691955 cites W2055607189 @default.
• W1996691955 cites W2057833130 @default.
• W1996691955 cites W2064158450 @default.
• W1996691955 cites W2065497508 @default.
• W1996691955 cites W2066758344 @default.
• W1996691955 cites W2069506896 @default.
• W1996691955 cites W2070035569 @default.
• W1996691955 cites W2071065914 @default.
• W1996691955 cites W2072565033 @default.
• W1996691955 cites W2074880155 @default.
• W1996691955 cites W2078274527 @default.
• W1996691955 cites W2079133298 @default.
• W1996691955 cites W2082345487 @default.
• W1996691955 cites W2082712943 @default.
• W1996691955 cites W2083323519 @default.
• W1996691955 cites W2085256740 @default.
• W1996691955 cites W2085336624 @default.
• W1996691955 cites W2086957099 @default.
• W1996691955 cites W2087006788 @default.
• W1996691955 cites W2087878614 @default.
• W1996691955 cites W2089021470 @default.
• W1996691955 cites W2094559512 @default.
• W1996691955 cites W2094642658 @default.
• W1996691955 cites W2097288467 @default.
• W1996691955 cites W2100665654 @default.
• W1996691955 cites W2108812250 @default.
• W1996691955 cites W2116396555 @default.
• W1996691955 cites W2116667141 @default.
• W1996691955 cites W2127149823 @default.
• W1996691955 cites W2133224281 @default.
• W1996691955 cites W2133416961 @default.
• W1996691955 cites W2133842167 @default.
• W1996691955 cites W2135960212 @default.
• W1996691955 cites W2140668939 @default.
• W1996691955 cites W2143981217 @default.
• W1996691955 cites W2150697053 @default.

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