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Heterolysis alkyl bromides

Fig. 2.15. Thermodynamic cycle for calculating the free energy of heterolysis of alkyl bromides in solution (AGhet J from free energies in the gas phase AGS refers to the free energy of solvation, AGhet refers to the free energy of heterolysis in the gas phase. Fig. 2.15. Thermodynamic cycle for calculating the free energy of heterolysis of alkyl bromides in solution (AGhet J from free energies in the gas phase AGS refers to the free energy of solvation, AGhet refers to the free energy of heterolysis in the gas phase.
The formation of the heterocycle 1 from the xylylene-bis-phosphonium salt 2 and PCI3 proceeds via a detectable intermediate 3 in a cascade of condensation reactions that is terminated by spontaneous heterolysis of the last remaining P-Cl bond in a cyclic bis-ylide-substituted chlorophosphine formed (Scheme 1) [15]. The reaction scheme is applicable to an arsenic analogue of 1 [15] and to bis-phosphonio-benzophospholides with different triaryl-, aryl-alkyl- and aryl-vinyl-phosphonio groups [16, 18, 19], but failed for trialkylphosphonio-substituted cations here, insufficient acidity prohibited obviously quantitative deprotonation of the phosphonium salts, and only mixtures of products with unreacted starting materials were obtained [19]. The cations were isolated as chloride or bromide salts, but conversion of the anions by complexation with Lewis-acids or metathesis was easily feasible [16, 18, 19] and even salts with organometallic anions ([Co(CO)4] , [CpM(CO)3] (M=Mo, W) were accessible [20]. [Pg.179]


See other pages where Heterolysis alkyl bromides is mentioned: [Pg.250]    [Pg.99]   
See also in sourсe #XX -- [ Pg.63 ]




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