Citation: CAO Chen-Zhong, WU Ya-Xin. An Extended Istomin-Palm Model for Estimating the Enthalpies of Formation of the Two-Direction Extending Compounds R1-Y-R2[J]. Acta Physico-Chimica Sinica, ;2013, 29(01): 35-42. doi: 10.3866/PKU.WHXB201210261 shu

An Extended Istomin-Palm Model for Estimating the Enthalpies of Formation of the Two-Direction Extending Compounds R1-Y-R2

CAO Chen-Zhong ^1, ,
WU Ya-Xin ^1,2

1.
1 Hunan Provincial University Key Laboratory of QSAR/QSPR, Key Laboratory of Theoretical Chemistry and Molecular Simulation of Ministry of Education, School of Chemistry and Chemical Engineering, Hunan University of Science and Technology, Xiangtan 411201, Hunan Province, P. R. China;
2 School of Chemistry and Chemical Engineering, Central South University, Changsha 410083, P. R. China

Received Date: 3 July 2012
Available Online: 26 October 2012
Fund Project: 国家自然科学基金(21072053) (21072053)湖南省教育厅科研基金(10K025)资助项目 (10K025)

Istomin and Palm proposed a model, Δ_fH⁰(RX)=h[R]+h[X]+φ[R]φ[X], (the h[R] and h[X] are the contributions of alkyl R and substituent X to the Δ_fH⁰(RX), respectively. φ[R]φ[X] represents the interaction of alkyl R and substituent X), to express the enthalpies of formation of monoderivatives of hydrocarbons Δ_fH⁰(RX). However, in two-direction extending compounds R1-Y-R2, the Y substituent is attached to two alkyl groups (R1 and R2), and the intramolecular interactions are more complicated than that in monosubstituted alkanes. Thus, the Istomin-Palm model must be modified. In this work, the interactions among Y, R1, and R2 contributing to the enthalpy of formation, Δ_fH⁰(R1-Y-R2), are divided into three parts: the interaction between R1Y and R2(φ[R2]φ[R1Y]), the interaction between YR2 and R1 (φ[R1]φ[YR2]), and the interaction between R1 and R2 (ψ[R1]ψ[R2]). These three interactions replace the φ[R]φ[X] term, and a new extended Istomin-Palm model, Δ_fH⁰(R1-Y-R2)=h[R1]+h[R2]+h[Y] +φ[R1]φ[YR2]+φ[R2]φ[R1Y]+ψ[R1]ψ[R2], is proposed. In this model, h[Y] is the contribution of substituent Y to Δ_fH⁰(R1-Y-R2). The h[R1] and h[R2] terms are the contributions of alkyls R1 and R2 to Δ_fH⁰(R1-Y-R2). The last three terms are the total contribution of interactions among Y, R1, and R2. Furthermore, the interaction potential index IPI(X) reported in our recent work (Wu, Y. X.; Cao, C. Z.; Yuan, H. Chin. J. Chem. Phys. 2012, 25 (2), 153.) was employed to express the intrinsic interaction of Y with alkyl groups (φ[Y]), and two general expressions were established to estimate Δ_fH⁰, in which one is for thioethers, secondary amines, ethers, and ketones, and the other is for esters. These two estimating equations give results, which are as accurate as G3 and G3MP2 models in calculating Δ_fH⁰ for R1-Y-R2 compounds. Moreover, our method avoids time consuming calculations.
- Enthalpy of formation,
- Substituent,
- Interaction,
- Two-direction extending compound,
- Interaction potential index
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