Effect of Intramolecular Hydrogen Bonds on the Gas-Phase Basicity of Guanidines

Zoran Glasovac; Mirjana Eckert-Maksić

doi:10.1071/CH14182

RESEARCH ARTICLE

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Effect of Intramolecular Hydrogen Bonds on the Gas-Phase Basicity of Guanidines

Zoran Glasovac ^A ^B and Mirjana Eckert-Maksić ^A

+ Author Affiliations

- Author Affiliations

^A Laboratory for Physical-Organic Chemistry, Division of Organic Chemistry and Biochemistry, Ruđer Bošković Institute, HR-10000 Zagreb, Croatia.

^B Corresponding author. Email: glasovac@irb.hr

Australian Journal of Chemistry 67(7) 1056-1062 https://doi.org/10.1071/CH14182
Submitted: 29 March 2014 Accepted: 8 May 2014 Published: 12 June 2014

Abstract

Three series of novel trisubstituted guanidines containing at least one hydrogen bond accepting (HBA) group were modelled using B3LYP/6–311+G(2df,p)//B3LYP/6–31G(d) calculations. Their structure was modified by incorporating a variety of different HBA groups covering a wide range of hydrogen bond strengths. Calculated gas-phase basicities (GBs) ranged from 1035 to 1181 kJ mol^–1 depending on the nature of the substituent. To rationalise changes in the GB, a correlation of GB against two independent variables (pK_HB and σ^4B) was conducted where pK_HB served as the descriptor of the hydrogen bond strength and σ^4B was introduced to describe changes in the GBs in the open-chain model systems, i.e. in the absence of intramolecular hydrogen bond (IMHB), caused by the electronic effect of the propyl-HBA substituent. A very good correlation of the calculated gas-phase basicities against these two independent variables was established for all three sets of the bases.

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Effect of Intramolecular Hydrogen Bonds on the Gas-Phase Basicity of Guanidines

Abstract

References

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