13607-35-7Relevant academic research and scientific papers
A MEASURE OF CHARGE TRANSFER (ρ) VERSUS A MEASURE OF BOND TIGHTNESS (ρij) IN THE TRANSITION STATE.
Lee, Ikchoon,Kang, Han Keun
, p. 1183 - 1186 (1987)
An example has been presented in which ρ is only a measure of charge transfer whereas ρij serves as a measure of bond tightness in the transition state.
Nucleophilic Substitution Reaction of Phenylmethanesulfonyl Halides with Anilines
Lee, Ikchoon,Kang, Han Keun,Lee, Hai Whang
, p. 7472 - 7477 (2007/10/02)
Kinetic studies on the nucleophilic substitution reaction of Y-substituted phenylmethanesulfonyl halides with X-substituted anilines in methanol-acetonitrile have been carried out in order to elucidate the reaction mechanism.The phenylmethanesulfonyl fluorides (PSF) had markedly lower rates and smaller magnitudes of ρX and ρY values compared with those for the chlorides (PSC).On the contrary, however, the magnitude of the cross-interaction constant ρXY was greater for PSF than for PSC, so that the degree of bond making in the transition state is actually greater in the reaction of PSF as compared with that for PSC.We have thus demonstrated that extensive charge transfer from a nucleophile to a substrate does not necessarily mean a tight bond in the transition state.Moreover the nonzero ρXY values obtained for both PSC and PSF are taken as evidence in support of a common, associative SN2 mechanism for the two halides.
