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

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Abstract

Nucleophilicity and CO2 fixation ability of the ylides of phosphorous, sulfur and nitrogen have been assessed using DFT calculations at M06-2X/6-311++G(d,p)//M06-2X/6-31+G(d) level. Nucleophilicity of 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 for the S-ylides. Two key geometrical parameters, condensed Fukui function (fk−) and Gibbs free energy of reaction (ΔGr) for the ylide-CO2 adducts have also been calculated. In absence of steric effect around the ylidic C-atom and any other secondary interaction, binding energy of the CO2-adducts of all the three types of ylides has a good linear correlation with the nucleophilicity. Nucleophilicity of a P-ylide increases when electron-donating groups are introduced as substituents on both P and the ylidic C-atom. An electron-withdrawing group on the same sites reduces nucleophilicity. Free ylides have higher nucleophilicity than their CO2 adducts.

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Acknowledgements

Financial support from SERB, India (Grant No. EMR/2016/007883) is gratefully acknowledged.

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Authors and Affiliations

  1. Department of Chemistry, Gauhati University, Guwahati, Assam, 781 001, India

    Dipanjali Pathak & Prodeep Phukan

  2. Department of Chemistry, M. C. College, Barpeta, Assam, 781 301, India

    Sanjib Deuri

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  1. Dipanjali Pathak
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  2. Sanjib Deuri
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Correspondence to Prodeep Phukan.

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Pathak, D., Deuri, S. & Phukan, P. Nucleophilicity and CO2 fixation ability of phosphorus, nitrogen and sulfur ylides: insights on stereoelectronic factors from DFT study. J Chem Sci 133, 127 (2021). https://doi.org/10.1007/s12039-021-01983-6

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