FRINK Linked Data Fragments server

Matches in SemOpenAlex for { <https://semopenalex.org/work/W2108205593> ?p ?o ?g. }

• W2108205593 endingPage "770" @default.
• W2108205593 startingPage "759" @default.
• W2108205593 abstract "Ketone complexes [CpM(CO)2(PR3)(η1-Et2CO)]+BAr′4− (R = Ph or Me; M = Mo or W) were prepared from hydride transfer from Cp(CO)2(PR3)MH to Ph3C+BAr′4− [Ar′ = 3,5-bis(trifluoromethyl)phenyl] in the presence of 3-pentanone. These ketone complexes are catalyst precursors for hydrogenation of Et2CO under mild conditions (23 °C, <4 atm H2). Analogous catalytic hydrogenations are obtained from reaction of the PCy3 complexes Cp(CO)2(PCy3)MH with Ph3C+BAr′4−. The proposed mechanism involves displacement of the ketone by H2, producing a cationic metal dihydride [CpM(CO)2(PR3)(H)2]+. Proton transfer from the dihydride gives a protonated ketone, followed by hydride transfer from the neutral metal hydride CpM(CO)2(PR3)H to produce the alcohol complex [CpM(CO)2(PR3)(Et2CHOH)]+. The free alcohol product is released from the metal through displacement by H2 or ketone, completing the catalytic cycle. In most cases, conversion of the ketone or alcohol complexes to the dihydride is the turnover-limiting step of the catalytic cycle, with ketone and alcohol complexes being observed during the reaction. For reactions using the W–PCy3 system, the dihydride [CpW(CO)2(PCy3)(H)2]+ is observed as the resting state of the catalytic process. Proton transfer is slow and becomes turnover-limiting in this case. The Mo catalysts are more active than W, and the dependence on phosphine is PCy3 > PPh3 > PMe3. The turnover rates are slow, with the fastest initial rate of about 2 turnovers per hour found for the Mo–PCy3 system. This ionic hydrogenation mechanism does not require coordination of the ketone to the metal for the hydrogenation, thus differing from traditional mechanisms where coordination of a ketone to a metal precedes insertion of the ketone into a M–H bond." @default.
• W2108205593 created "2016-06-24" @default.
• W2108205593 creator A5003240669 @default.
• W2108205593 creator A5022980951 @default.
• W2108205593 date "2002-01-21" @default.
• W2108205593 modified "2023-10-18" @default.
• W2108205593 title "Catalytic ionic hydrogenations of ketones using molybdenum and tungsten complexesBased on the presentation given at Dalton Discussion No. 4, 10–13th January 2002, Kloster Banz, Germany." @default.
• W2108205593 cites W1578368725 @default.
• W2108205593 cites W1968670039 @default.
• W2108205593 cites W1977870471 @default.
• W2108205593 cites W1982160044 @default.
• W2108205593 cites W1988084277 @default.
• W2108205593 cites W1990664188 @default.
• W2108205593 cites W1991004860 @default.
• W2108205593 cites W1991653595 @default.
• W2108205593 cites W1994884720 @default.
• W2108205593 cites W1995993593 @default.
• W2108205593 cites W1996876949 @default.
• W2108205593 cites W2005257160 @default.
• W2108205593 cites W2006117836 @default.
• W2108205593 cites W2007230272 @default.
• W2108205593 cites W2009512006 @default.
• W2108205593 cites W2012028316 @default.
• W2108205593 cites W2012443214 @default.
• W2108205593 cites W2012543217 @default.
• W2108205593 cites W2013160605 @default.
• W2108205593 cites W2015253591 @default.
• W2108205593 cites W2015632099 @default.
• W2108205593 cites W2018573899 @default.
• W2108205593 cites W2019002493 @default.
• W2108205593 cites W2023174370 @default.
• W2108205593 cites W2026620997 @default.
• W2108205593 cites W2028257896 @default.
• W2108205593 cites W2032905502 @default.
• W2108205593 cites W2033136910 @default.
• W2108205593 cites W2034626294 @default.
• W2108205593 cites W2036070960 @default.
• W2108205593 cites W2038860808 @default.
• W2108205593 cites W2040371083 @default.
• W2108205593 cites W2045782831 @default.
• W2108205593 cites W2048452974 @default.
• W2108205593 cites W2048871788 @default.
• W2108205593 cites W2049216879 @default.
• W2108205593 cites W2049439497 @default.
• W2108205593 cites W2050828896 @default.
• W2108205593 cites W2052846008 @default.
• W2108205593 cites W2057094363 @default.
• W2108205593 cites W2062808723 @default.
• W2108205593 cites W2065569278 @default.
• W2108205593 cites W2068210412 @default.
• W2108205593 cites W2070664808 @default.
• W2108205593 cites W2071690550 @default.
• W2108205593 cites W2074422220 @default.
• W2108205593 cites W2075587187 @default.
• W2108205593 cites W2077427344 @default.
• W2108205593 cites W2078523968 @default.
• W2108205593 cites W2082456625 @default.
• W2108205593 cites W2083127056 @default.
• W2108205593 cites W2084277985 @default.
• W2108205593 cites W2085856850 @default.
• W2108205593 cites W2088834747 @default.
• W2108205593 cites W2091449628 @default.
• W2108205593 cites W2091702998 @default.
• W2108205593 cites W2103506671 @default.
• W2108205593 cites W2108624258 @default.
• W2108205593 cites W2115492271 @default.
• W2108205593 cites W2143504470 @default.
• W2108205593 cites W2323424559 @default.
• W2108205593 cites W2343767939 @default.
• W2108205593 cites W2949143415 @default.
• W2108205593 cites W2949170092 @default.
• W2108205593 cites W2951575665 @default.
• W2108205593 cites W2951694027 @default.
• W2108205593 cites W2952709866 @default.
• W2108205593 cites W3005352396 @default.
• W2108205593 cites W401052397 @default.
• W2108205593 cites W638283757 @default.
• W2108205593 cites W66888068 @default.
• W2108205593 doi "https://doi.org/10.1039/b107754f" @default.
• W2108205593 hasPublicationYear "2002" @default.
• W2108205593 type Work @default.
• W2108205593 sameAs 2108205593 @default.
• W2108205593 citedByCount "68" @default.
• W2108205593 countsByYear W21082055932012 @default.
• W2108205593 countsByYear W21082055932013 @default.
• W2108205593 countsByYear W21082055932014 @default.
• W2108205593 countsByYear W21082055932015 @default.
• W2108205593 countsByYear W21082055932016 @default.
• W2108205593 countsByYear W21082055932017 @default.
• W2108205593 countsByYear W21082055932018 @default.
• W2108205593 countsByYear W21082055932019 @default.
• W2108205593 countsByYear W21082055932020 @default.
• W2108205593 countsByYear W21082055932021 @default.
• W2108205593 crossrefType "journal-article" @default.
• W2108205593 hasAuthorship W2108205593A5003240669 @default.
• W2108205593 hasAuthorship W2108205593A5022980951 @default.
• W2108205593 hasConcept C145148216 @default.
• W2108205593 hasConcept C155647269 @default.

• next