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• W2024330984 endingPage "7080" @default.
• W2024330984 startingPage "7071" @default.
• W2024330984 abstract "The ruthenium(II) tris-acetonitrile complex [(triphos)Ru(MeCN)3]BPh4 (1) is an extremely efficient catalyst precursor for the regioselective hydrogenation of benzo[b]thiophene (BT) to 2,3-dihydrobenzo[b]thiophene (DHBT) in homogeneous phase under mild reaction conditions (THF, 40−100 °C, 1−30 bar H2) [triphos = MeC(CH2PPh2)3]. At 30 bar of H2 and 100 °C, BT is converted to DHBT with an average rate of 500 mol of product (mol of cat)-1 h-1. During the catalytic reactions with PH2 > 5 bar, the acetonitrile ligands in 1 are transformed into a mixture of NHEt2, NEt3, and NH3, while the termination ruthenium products are the monohydrido complexes [(triphos)Ru(H)(NH3)2]BPh4, [(triphos)Ru(H)(NH3)(NH2Et)]BPh4, and [(triphos)Ru(H)(NH3)(η1-S-DHBT)]BPh4. Below 5 bar of H2, no hydrogenation of MeCN occurs and all of the ruthenium is recovered as [(triphos)Ru(H)(NCMe)(η1-S-DHBT)]BPh4. All of these Ru(II) hydrido complexes catalyze the hydrogenation of BT to DHBT as efficiently as 1. The substitution of D2 for H2 in a catalytic reaction shows that BT is selectively cis-deuterated to DHBT-d2 with no deuterium enrichment in either the unreacted BT or the arene ring of DHBT. Water in the reaction mixture decreases the hydrogenation rate of BT due to the formation of the μ-OH and acetate Ru(II) complexes [(triphos)Ru(μ-OH)3Ru(triphos)]BPh4 and [(triphos)Ru(O2CCH3)(OH2)]BPh4, which are catalytically inactive. The acetate complex is suggested to form via hydration of a MeCN ligand in the catalyst precursor. Catalytic runs at 30 and 2 bar of H2 were studied in situ by high-pressure NMR spectroscopy. The kinetics of the hydrogenation of BT in the presence of 1 were studied by gas adsorption techniques at different catalyst, substrate, and dihydrogen concentrations and at different temperatures. The kinetic data together with all of the other evidence accumulated allowed us to deduce a catalytic cycle in which the reversible dissociation of the thioether product from the metal center in the catalyst [(triphos)RuH]+ is a rate-limiting step. A comparison of the hydrogenation reactions of BT catalyzed by either the Ru(II) 14e- fragment [(triphos)RuH]+ or the Ru(0) 16e- fragment [(triphos)RuH]- has provided some clues to unravel a number of mechanistic aspects of the HDS of thiophenes over single-component catalysts. In particular, the occurrence of either hydrogenation to thioether or hydrogenolysis to thiol has been related with the metal basicity." @default.
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• W2024330984 date "1999-07-16" @default.
• W2024330984 modified "2023-10-11" @default.
• W2024330984 title "Mimicking the HDS Activity of Ruthenium-Based Catalysts 2: The Hydrogenation of Benzo[<i>b</i>]thiophene to 2,3-Dihydrobenzo[<i>b</i>]thiophene" @default.
• W2024330984 cites W1479832974 @default.
• W2024330984 cites W1508000372 @default.
• W2024330984 cites W1964553820 @default.
• W2024330984 cites W1966321274 @default.
• W2024330984 cites W1968490532 @default.
• W2024330984 cites W1969547563 @default.
• W2024330984 cites W1969691757 @default.
• W2024330984 cites W1970593603 @default.
• W2024330984 cites W1972786714 @default.
• W2024330984 cites W1976979009 @default.
• W2024330984 cites W1980526290 @default.
• W2024330984 cites W1984006462 @default.
• W2024330984 cites W1985656448 @default.
• W2024330984 cites W1988092665 @default.
• W2024330984 cites W1988926593 @default.
• W2024330984 cites W1989570422 @default.
• W2024330984 cites W1992969490 @default.
• W2024330984 cites W1993077404 @default.
• W2024330984 cites W1996252712 @default.
• W2024330984 cites W1999545048 @default.
• W2024330984 cites W2003142961 @default.
• W2024330984 cites W2003987213 @default.
• W2024330984 cites W2004374339 @default.
• W2024330984 cites W2010168056 @default.
• W2024330984 cites W2011056512 @default.
• W2024330984 cites W2013877033 @default.
• W2024330984 cites W2016415314 @default.
• W2024330984 cites W2020351248 @default.
• W2024330984 cites W2032911263 @default.
• W2024330984 cites W2033029821 @default.
• W2024330984 cites W2033942388 @default.
• W2024330984 cites W2034742186 @default.
• W2024330984 cites W2034759398 @default.
• W2024330984 cites W2037426601 @default.
• W2024330984 cites W2038489341 @default.
• W2024330984 cites W2039057824 @default.
• W2024330984 cites W2039893577 @default.
• W2024330984 cites W2040371083 @default.
• W2024330984 cites W2040821099 @default.
• W2024330984 cites W2043273519 @default.
• W2024330984 cites W2045061977 @default.
• W2024330984 cites W2046198633 @default.
• W2024330984 cites W2049479941 @default.
• W2024330984 cites W2049800042 @default.
• W2024330984 cites W2051085799 @default.
• W2024330984 cites W2051614906 @default.
• W2024330984 cites W2055120311 @default.
• W2024330984 cites W2055899359 @default.
• W2024330984 cites W2061018200 @default.
• W2024330984 cites W2062492817 @default.
• W2024330984 cites W2064491091 @default.
• W2024330984 cites W2066217799 @default.
• W2024330984 cites W2067968372 @default.
• W2024330984 cites W2069061312 @default.
• W2024330984 cites W2071354191 @default.
• W2024330984 cites W2076764886 @default.
• W2024330984 cites W2077848275 @default.
• W2024330984 cites W2080503445 @default.
• W2024330984 cites W2083263654 @default.
• W2024330984 cites W2084427018 @default.
• W2024330984 cites W2085208616 @default.
• W2024330984 cites W2088101752 @default.
• W2024330984 cites W2094686194 @default.
• W2024330984 cites W2105959912 @default.
• W2024330984 cites W2116504877 @default.
• W2024330984 cites W2144707381 @default.
• W2024330984 cites W2145179439 @default.
• W2024330984 cites W2258630804 @default.
• W2024330984 cites W247459632 @default.
• W2024330984 cites W2888847892 @default.
• W2024330984 cites W2949081413 @default.
• W2024330984 cites W2949997291 @default.
• W2024330984 cites W2952739866 @default.
• W2024330984 cites W2952922230 @default.
• W2024330984 cites W4211133984 @default.
• W2024330984 cites W4236411977 @default.
• W2024330984 cites W4252215861 @default.
• W2024330984 doi "https://doi.org/10.1021/ja983224e" @default.
• W2024330984 hasPublicationYear "1999" @default.
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