Matches in SemOpenAlex for { <https://semopenalex.org/work/W2015587924> ?p ?o ?g. }
- W2015587924 endingPage "9402" @default.
- W2015587924 startingPage "9393" @default.
- W2015587924 abstract "Theoretical calculations on aggregation of nBuLi/lithium aminoalkoxide superbases, such as nBuLi/LiDMAE (LiDMAE = Me2N(CH2)2OLi) and nBuLi/LiPM (LiPM = Li-N-methyl-2-pyrrolidine methoxide) in gas phase and solution are reported. The combination of equimolar amounts of each component in hexane induced unusual reactivity of the resulting superbase, which remains misunderstood. In order to elucidate the corresponding reaction mechanisms, it is imperative to get a deeper insight into the energetics of aggregation and the effect of the medium on equilibrium constants. In the present study, we compute and compare the stability of (nBuLi)n, (LiPM)n, and equimolecular mixed aggregates (nBuLi:LiPM)n in gas phase, hexane, and THF. Calculations have been carried out at the density functional theory level (B3LYP/6-31G(d)) using continuum and discrete continuum models of solvation. Higher-level calculations (MP2/aug-ccpVQZ) have been done in some cases for test purposes. Enthalpic and entropic contributions have been discussed and were shown to play an opposite role in hexane (or gas phase) and THF. The characteristics of LiPM and mixed nBuLi/LiPM solutions are found to be significantly different from those of nBuLi solutions. These calculations are in accordance with experimental data in both hexane and THF. Further comparison of theoretical and experimental results for gas-phase Li+−THF and Li+−DME complexes has enabled a discussion on computational errors for entropic contributions in THF. The value for the release of a THF solvent molecule is proposed to be ΔS ≈ 23 eu. These results provide new insights to the aggregation of organolithium compounds in solution and will be useful for the investigation of other systems." @default.
- W2015587924 created "2016-06-24" @default.
- W2015587924 creator A5019694657 @default.
- W2015587924 creator A5046040186 @default.
- W2015587924 creator A5063906596 @default.
- W2015587924 creator A5070199646 @default.
- W2015587924 date "2008-10-28" @default.
- W2015587924 modified "2023-10-16" @default.
- W2015587924 title "A Theoretical Study on <i>n</i>BuLi/Lithium Aminoalkoxide Aggregation in Hexane and THF" @default.
- W2015587924 cites W1530873460 @default.
- W2015587924 cites W1534493785 @default.
- W2015587924 cites W1963848572 @default.
- W2015587924 cites W1965658448 @default.
- W2015587924 cites W1966132341 @default.
- W2015587924 cites W1966424505 @default.
- W2015587924 cites W1967453137 @default.
- W2015587924 cites W1967766788 @default.
- W2015587924 cites W1969384555 @default.
- W2015587924 cites W1974140657 @default.
- W2015587924 cites W1975309920 @default.
- W2015587924 cites W1979827928 @default.
- W2015587924 cites W1980875937 @default.
- W2015587924 cites W1981566548 @default.
- W2015587924 cites W1988049269 @default.
- W2015587924 cites W1989890074 @default.
- W2015587924 cites W1992707487 @default.
- W2015587924 cites W1993383767 @default.
- W2015587924 cites W1994143888 @default.
- W2015587924 cites W1997151511 @default.
- W2015587924 cites W2001851554 @default.
- W2015587924 cites W2002430490 @default.
- W2015587924 cites W2002636242 @default.
- W2015587924 cites W2003254952 @default.
- W2015587924 cites W2003638230 @default.
- W2015587924 cites W2004057173 @default.
- W2015587924 cites W2010888160 @default.
- W2015587924 cites W2012449633 @default.
- W2015587924 cites W2014030314 @default.
- W2015587924 cites W2016126091 @default.
- W2015587924 cites W2020985307 @default.
- W2015587924 cites W2023340784 @default.
- W2015587924 cites W2024632976 @default.
- W2015587924 cites W2025169345 @default.
- W2015587924 cites W2025578670 @default.
- W2015587924 cites W2026467865 @default.
- W2015587924 cites W2027436047 @default.
- W2015587924 cites W2028943451 @default.
- W2015587924 cites W2029747014 @default.
- W2015587924 cites W2030206358 @default.
- W2015587924 cites W2031605136 @default.
- W2015587924 cites W2032920583 @default.
- W2015587924 cites W2033051702 @default.
- W2015587924 cites W2033505070 @default.
- W2015587924 cites W2035200946 @default.
- W2015587924 cites W2035548211 @default.
- W2015587924 cites W2036337070 @default.
- W2015587924 cites W2041036055 @default.
- W2015587924 cites W2046655723 @default.
- W2015587924 cites W2048608341 @default.
- W2015587924 cites W2048692916 @default.
- W2015587924 cites W2051952262 @default.
- W2015587924 cites W2052525478 @default.
- W2015587924 cites W2052858136 @default.
- W2015587924 cites W2053198993 @default.
- W2015587924 cites W2054991371 @default.
- W2015587924 cites W2055423133 @default.
- W2015587924 cites W2055831544 @default.
- W2015587924 cites W2060576956 @default.
- W2015587924 cites W2062609683 @default.
- W2015587924 cites W2062788624 @default.
- W2015587924 cites W2064784056 @default.
- W2015587924 cites W2065420621 @default.
- W2015587924 cites W2071579808 @default.
- W2015587924 cites W2072315853 @default.
- W2015587924 cites W2072411932 @default.
- W2015587924 cites W2073140295 @default.
- W2015587924 cites W2073471248 @default.
- W2015587924 cites W2079195295 @default.
- W2015587924 cites W2081677409 @default.
- W2015587924 cites W2086532083 @default.
- W2015587924 cites W2091953824 @default.
- W2015587924 cites W2095522644 @default.
- W2015587924 cites W2099852092 @default.
- W2015587924 cites W2131022633 @default.
- W2015587924 cites W2133722243 @default.
- W2015587924 cites W2135218291 @default.
- W2015587924 cites W2146767122 @default.
- W2015587924 cites W2163288825 @default.
- W2015587924 cites W2167628643 @default.
- W2015587924 cites W2345883726 @default.
- W2015587924 cites W2604941986 @default.
- W2015587924 cites W2950274023 @default.
- W2015587924 cites W2950887315 @default.
- W2015587924 cites W2951415722 @default.
- W2015587924 cites W2951783958 @default.
- W2015587924 cites W2952971187 @default.
- W2015587924 cites W4236801525 @default.
- W2015587924 cites W2952644721 @default.