Matches in SemOpenAlex for { <https://semopenalex.org/work/W2774243548> ?p ?o ?g. }
- W2774243548 endingPage "11" @default.
- W2774243548 startingPage "2" @default.
- W2774243548 abstract "The reaction mechanism for hydrosilylation of imines and alkynes catalyzed by a nitrido complex of high-valent Ru(VI) has been studied using density functional theory. Four different reaction routes for RuVIN complex catalyzed hydrosilylation have been probed in detail, spanning those involving N, RuVI, or RuIII as active center in activating SiH bonds. The activation of SiH bond at the nitrido ligand can be discounted because they would lead to large activation barrier for reduction of imines and alkynes. Our computational results support an ionic outer-sphere mechanism involving silane initially binding with ruthenium metal. This proposed ionic outer-sphere mechanism is characterized by a rate-determining SiH bond cleavage upon imines nitrogen or alkynes carbon atoms backside attacking the silane-ruthenium complex, featuring a SN[email protected] transition state. In addition, we found organic substrate is crucial in controlling the catalytic cycle. With imines, the ionic outer-sphere cycle occurs at the high-valent RuVI metal center is preferable. The highest energy barrier must overcome is 21.9 kcal/mol. With alkynes, the low-valent RuIII complex formed by NN coupling of RuVIN complex is the real catalytic species. The rate-determining energy barrier is calculated to be 12.7 kcal/mol." @default.
- W2774243548 created "2017-12-22" @default.
- W2774243548 creator A5014043195 @default.
- W2774243548 creator A5016947466 @default.
- W2774243548 creator A5018130586 @default.
- W2774243548 creator A5072650586 @default.
- W2774243548 date "2018-06-01" @default.
- W2774243548 modified "2023-09-24" @default.
- W2774243548 title "Nitrido complex of high-valent Ru(VI) -catalyzed reduction of imines and alkynes with hydrosilanes: A theoretical study of the reaction mechanism" @default.
- W2774243548 cites W1529004524 @default.
- W2774243548 cites W1581414230 @default.
- W2774243548 cites W1793500466 @default.
- W2774243548 cites W1964837435 @default.
- W2774243548 cites W1964885234 @default.
- W2774243548 cites W1966182479 @default.
- W2774243548 cites W1966203171 @default.
- W2774243548 cites W1968685369 @default.
- W2774243548 cites W1971275758 @default.
- W2774243548 cites W1971758201 @default.
- W2774243548 cites W1972601400 @default.
- W2774243548 cites W1974565407 @default.
- W2774243548 cites W1975956534 @default.
- W2774243548 cites W1982452541 @default.
- W2774243548 cites W1982463068 @default.
- W2774243548 cites W1983034638 @default.
- W2774243548 cites W1983503649 @default.
- W2774243548 cites W1983656816 @default.
- W2774243548 cites W1983998320 @default.
- W2774243548 cites W1984614201 @default.
- W2774243548 cites W1986665459 @default.
- W2774243548 cites W1986818607 @default.
- W2774243548 cites W1988283781 @default.
- W2774243548 cites W1989767668 @default.
- W2774243548 cites W1989939289 @default.
- W2774243548 cites W1992032739 @default.
- W2774243548 cites W1992775007 @default.
- W2774243548 cites W1995196736 @default.
- W2774243548 cites W1996455423 @default.
- W2774243548 cites W1996915121 @default.
- W2774243548 cites W1997683728 @default.
- W2774243548 cites W1998580952 @default.
- W2774243548 cites W2000218124 @default.
- W2774243548 cites W2002007474 @default.
- W2774243548 cites W2002271411 @default.
- W2774243548 cites W2003474302 @default.
- W2774243548 cites W2003639645 @default.
- W2774243548 cites W2006487731 @default.
- W2774243548 cites W2011215428 @default.
- W2774243548 cites W2015036859 @default.
- W2774243548 cites W2016913560 @default.
- W2774243548 cites W2017267600 @default.
- W2774243548 cites W2017408363 @default.
- W2774243548 cites W2017711124 @default.
- W2774243548 cites W2021447121 @default.
- W2774243548 cites W2022314825 @default.
- W2774243548 cites W2022505941 @default.
- W2774243548 cites W2023271753 @default.
- W2774243548 cites W2023875511 @default.
- W2774243548 cites W2030443596 @default.
- W2774243548 cites W2031776284 @default.
- W2774243548 cites W2033410267 @default.
- W2774243548 cites W2033874225 @default.
- W2774243548 cites W2039908571 @default.
- W2774243548 cites W2041158998 @default.
- W2774243548 cites W2041572709 @default.
- W2774243548 cites W2041835823 @default.
- W2774243548 cites W2041885115 @default.
- W2774243548 cites W2042887158 @default.
- W2774243548 cites W2043350468 @default.
- W2774243548 cites W2044490585 @default.
- W2774243548 cites W2044591029 @default.
- W2774243548 cites W2047138685 @default.
- W2774243548 cites W2047817641 @default.
- W2774243548 cites W2049442413 @default.
- W2774243548 cites W2051784722 @default.
- W2774243548 cites W2053478604 @default.
- W2774243548 cites W2055946588 @default.
- W2774243548 cites W2058282121 @default.
- W2774243548 cites W2059530602 @default.
- W2774243548 cites W2059557791 @default.
- W2774243548 cites W2060137387 @default.
- W2774243548 cites W2061297570 @default.
- W2774243548 cites W2063347152 @default.
- W2774243548 cites W2066747456 @default.
- W2774243548 cites W2067006720 @default.
- W2774243548 cites W2074286899 @default.
- W2774243548 cites W2074420333 @default.
- W2774243548 cites W2075072091 @default.
- W2774243548 cites W2075990257 @default.
- W2774243548 cites W2076087133 @default.
- W2774243548 cites W2078089048 @default.
- W2774243548 cites W2079667104 @default.
- W2774243548 cites W2082712943 @default.
- W2774243548 cites W2085389876 @default.
- W2774243548 cites W2086780143 @default.
- W2774243548 cites W2090476367 @default.
- W2774243548 cites W2093562036 @default.
- W2774243548 cites W2093575737 @default.