• Nucleophilicity and CO2 fixation ability of phosphorus, nitrogen and sulfur ylides: insights on stereoelectronic factors from DFT study

    • Fulltext

       

        Click here to view fulltext PDF


      Permanent link:
      https://www.ias.ac.in/article/fulltext/jcsc/133/0127

    • Keywords

       

      Phosphorus ylide; sulfur ylide; nitrogen ylide; nucleophilicity index; CO2 fixation; substituent effect.

    • Abstract

       

      Nucleophilicity and CO2 fixation ability of the ylides of phosphorous, sulfur and nitrogen havebeen assessed using DFT calculations at M06-2X/6-311++G(d,p)//M06-2X/6-31+G(d) level. Nucleophilicityof 54 ylides and their CO2 adducts have been evaluated using a theoretical nucleophilicity index(N) which shows good linear correlation (R2 = 0.87) with Mayr’s experimental nucleophilicity parameter forthe S-ylides. Two key geometrical parameters, condensed Fukui function (fk-) and Gibbs free energy ofreaction (ΔGr) for the ylide-CO2 adducts have also been calculated. In absence of steric effect around theylidic C-atom and any other secondary interaction, binding energy of the CO2-adducts of all the three types ofylides has a good linear correlation with the nucleophilicity. Nucleophilicity of a P-ylide increases whenelectron-donating groups are introduced as substituents on both P and the ylidic C-atom. An electronwithdrawinggroup on the same sites reduces nucleophilicity. Free ylides have higher nucleophilicity thantheir CO2 adducts.

    • Graphical Abstract

       

    • Author Affiliations

       

      DIPANJALI PATHAK1 SANJIB DEURI2 PRODEEP PHUKAN1

      1. Department of Chemistry, Gauhati University, Guwahati, Assam 781 001, India
      2. Department of Chemistry, M. C. College, Barpeta, Assam 781 301, India
    • Dates

       
  • Journal of Chemical Sciences | News

© 2022-2023 Indian Academy of Sciences, Bengaluru.