Extended knowledge of 1038-95-5

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The kinetics of the reactions of benzhydrylium ions and quinone methides with eight tertiary phosphanes and two phosphites were investigated photometrically. The nucleophilicity parameters N and slope parameters s of these nucleophiles were derived according to the equation log/C 20C = S(N + E). Correlations of the nucleophilicity parameters N with pKHa and sigmap values as well as with the rate constants of reactions with other electrophiles are discussed. In some cases, equilibrium constants for the formation of phosphonium ions were measured, which allow one to determine the Marcus intrinsic barriers of DeltaG0 ? = 58 kJ mol-1 for the reactions of triarylphosphanes with benzhydrylium ions. The N parameters [5.51 for P(OPh)3, 10.36 for P(OBu)3, 14.33 for PPh3, 15.49 for PBu3, 18.39 for P(4-Me2NC6H4)3] are compared with the reactivities of other classes of nucleophiles (see, www.cup. uni-muenchen.de/oc/mayr).

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Reference:
Phosphine ligand,
Chiral phosphine ligands in asymmetric synthesis. Molecular structure and absolute configuration of (1,5-cyclooctadiene)-(2S,3S)-2,3-bis(diphenylphosphino)butanerhodium(I) perchlorate tetrahydrofuran solvate