FRINK Linked Data Fragments server

Matches in SemOpenAlex for { <https://semopenalex.org/work/W2011738251> ?p ?o ?g. }

• W2011738251 endingPage "1254" @default.
• W2011738251 startingPage "1245" @default.
• W2011738251 abstract "The five-coordinated 16-electron complex [Ru(Me)(dppe)2][OTf] (3) undergoes methane elimination at room temperature to afford the ortho-metalated species [(dppe){(C6H5)(C6H4)PCH2CH2P(C6H5)2}Ru][OTf] (7). Methane elimination, monitored using NMR spectroscopy, revealed no intermediate throughout the reaction. The NOE between Ru–Me protons and ortho phenyl protons and an agostic interaction trans to the methyl group were found in complex 3 by NMR spectroscopy, which form the basis for three plausible pathways for methane elimination and ortho metalation: pathway I (through spatial interaction), pathway II (through oxidative addition and reductive elimination), and pathway III (through agostic interaction). Methane elimination from complex 3 via pathway I was discounted, since it involves interactions through space and not through bonds. Moreover, the calculated energy barrier for the pathway I transition state was quite high (71.3 kcal/mol), which also indicates that this pathway is very unlikely. Furthermore, no spectroscopic evidence for oxidatively added seven-coordinated Ru(IV) species was found and the computed energy barrier of the transition state for pathway II was moderately high (41.1 kcal/mol), which suggests that this cannot be the right pathway for methane elimination and ortho-metalation of complex 3. On the other hand, indirect evidence in the form of chemical reactions point to the most plausible pathway for methane elimination, pathway III, via the intermediacy of a σ-CH4 complex that could not be found spectroscopically. DFT calculations at several levels on this pathway showed an initial low-barrier rearrangement through TS1 to a square-pyramidal intermediate wherein methyl and agostic C–H are cis to each other. Migration of hydrogen from agostic C–H and elimination of methane proceed through the transition state TS2, which retains a weak metal–H bonding through most parts of the reaction coordinate. Upon comparison of all three pathways, pathway III was found to be the most likely for methane elimination and ortho-metalation of complex 3." @default.
• W2011738251 created "2016-06-24" @default.
• W2011738251 creator A5006431795 @default.
• W2011738251 creator A5026540198 @default.
• W2011738251 creator A5067380080 @default.
• W2011738251 creator A5085379940 @default.
• W2011738251 date "2015-03-24" @default.
• W2011738251 modified "2023-09-27" @default.
• W2011738251 title "Implication of a σ-Methane Complex en Route to Elimination of Methane from a Ruthenium Complex: An Experimental and Theoretical Investigation" @default.
• W2011738251 cites W136347255 @default.
• W2011738251 cites W1963633034 @default.
• W2011738251 cites W1963761806 @default.
• W2011738251 cites W1967393692 @default.
• W2011738251 cites W1967941070 @default.
• W2011738251 cites W1969752293 @default.
• W2011738251 cites W1971483183 @default.
• W2011738251 cites W1971502329 @default.
• W2011738251 cites W1973755220 @default.
• W2011738251 cites W1974399206 @default.
• W2011738251 cites W1980017122 @default.
• W2011738251 cites W1981033537 @default.
• W2011738251 cites W1981368803 @default.
• W2011738251 cites W1983026194 @default.
• W2011738251 cites W1987581647 @default.
• W2011738251 cites W1988091937 @default.
• W2011738251 cites W1989727476 @default.
• W2011738251 cites W1990322519 @default.
• W2011738251 cites W1990888602 @default.
• W2011738251 cites W1991041500 @default.
• W2011738251 cites W1991222957 @default.
• W2011738251 cites W1991899258 @default.
• W2011738251 cites W1992811797 @default.
• W2011738251 cites W1994462433 @default.
• W2011738251 cites W1995462287 @default.
• W2011738251 cites W1996788682 @default.
• W2011738251 cites W1996846370 @default.
• W2011738251 cites W1999476828 @default.
• W2011738251 cites W2000714689 @default.
• W2011738251 cites W2001188508 @default.
• W2011738251 cites W2004127596 @default.
• W2011738251 cites W2005661768 @default.
• W2011738251 cites W2010189103 @default.
• W2011738251 cites W2013672217 @default.
• W2011738251 cites W2015109253 @default.
• W2011738251 cites W2015723183 @default.
• W2011738251 cites W2017033936 @default.
• W2011738251 cites W2021295250 @default.
• W2011738251 cites W2023271753 @default.
• W2011738251 cites W2038100915 @default.
• W2011738251 cites W2038533471 @default.
• W2011738251 cites W2039184375 @default.
• W2011738251 cites W2040172223 @default.
• W2011738251 cites W2040299058 @default.
• W2011738251 cites W2040669383 @default.
• W2011738251 cites W2041086195 @default.
• W2011738251 cites W2043510643 @default.
• W2011738251 cites W2049477866 @default.
• W2011738251 cites W2050023115 @default.
• W2011738251 cites W2054250029 @default.
• W2011738251 cites W2054704030 @default.
• W2011738251 cites W2055078295 @default.
• W2011738251 cites W2059672882 @default.
• W2011738251 cites W2061238945 @default.
• W2011738251 cites W2068617439 @default.
• W2011738251 cites W2069006374 @default.
• W2011738251 cites W2069503178 @default.
• W2011738251 cites W2072573552 @default.
• W2011738251 cites W2074664376 @default.
• W2011738251 cites W2076044769 @default.
• W2011738251 cites W2078301413 @default.
• W2011738251 cites W2081940375 @default.
• W2011738251 cites W2083332369 @default.
• W2011738251 cites W2090569379 @default.
• W2011738251 cites W2094009763 @default.
• W2011738251 cites W2094941017 @default.
• W2011738251 cites W2095562414 @default.
• W2011738251 cites W2099634855 @default.
• W2011738251 cites W2101584728 @default.
• W2011738251 cites W2119547517 @default.
• W2011738251 cites W2121500203 @default.
• W2011738251 cites W2129629428 @default.
• W2011738251 cites W2137485267 @default.
• W2011738251 cites W2143981217 @default.
• W2011738251 cites W2146929798 @default.
• W2011738251 cites W2148284063 @default.
• W2011738251 cites W2150195378 @default.
• W2011738251 cites W2150697053 @default.
• W2011738251 cites W2151220474 @default.
• W2011738251 cites W2168582519 @default.
• W2011738251 cites W2319266947 @default.
• W2011738251 cites W2332343612 @default.
• W2011738251 cites W2569525354 @default.
• W2011738251 cites W2949285876 @default.
• W2011738251 cites W3005068924 @default.
• W2011738251 cites W4237427979 @default.
• W2011738251 cites W4240035468 @default.
• W2011738251 doi "https://doi.org/10.1021/om501248v" @default.
• W2011738251 hasPublicationYear "2015" @default.

• next