Direct estimate of the strength of conjugation and hyperconjugation by the energy decomposition analysis method

Chemistry : a European Journal
Israel Fernandez, Gernot Frenking

Abstract

The intrinsic strength of pi interactions in conjugated and hyperconjugated molecules has been calculated using density functional theory by energy decomposition analysis (EDA) of the interaction energy between the conjugating fragments. The results of the EDA of the trans-polyenes H2C=CH-(HC=CH)n-CH=CH2 (n = 1-3) show that the strength of pi conjugation for each C=C moiety is higher than in trans-1,3-butadiene. The absolute values for the conjugation between Si=Si pi bonds are around two-thirds of the conjugation between C=C bonds but the relative contributions of DeltaE pi to DeltaE orb in the all-silicon systems are higher than in the carbon compounds. The pi conjugation between C=C and C=O or C=NH bonds in H2C=CH--C(H)=O and H2C=CH-C(H)=NH is comparable to the strength of the conjugation between C=C bonds. The pi conjugation in H2C=CH-C(R)=O decreases when R = Me, OH, and NH2 while it increases when R = halogen. The hyperconjugation in ethane is around a quarter as strong as the pi conjugation in ethyne. Very strong hyperconjugation is found in the central C-C bonds in cubylcubane and tetrahedranyltetrahedrane. The hyperconjugation in substituted ethanes X3C-CY3 (X,Y = Me, SiH3, F, Cl) is stronger than in the parent compoun...Continue Reading

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Citations

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Jun 11, 2014·Journal of Molecular Modeling·Judy I-Chia WuYirong Mo
May 28, 2014·Journal of Molecular Modeling·Monika Parafiniuk, Mariusz P Mitoraj
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Jan 26, 2017·Chemistry : a European Journal·Lennart T ScharfViktoria H Gessner
Jun 24, 2015·Journal of Computational Chemistry·Megha AnandJudy I-Chia Wu
Mar 3, 2007·Faraday Discussions·Israel Fernández, Gernot Frenking
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Aug 24, 2012·Chemistry : a European Journal·Israel FernándezFernando P Cossío
Apr 25, 2007·Chemistry : a European Journal·Israel Fernández, Gernot Frenking
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Jun 30, 2009·Chemistry : a European Journal·Wei WuYirong Mo
Oct 24, 2009·Chemistry : a European Journal·Israel FernándezFernando P Cossío
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May 26, 2009·Chemphyschem : a European Journal of Chemical Physics and Physical Chemistry·David AsturiolIstván Mayer
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