Separation of ground state and transition state effects in intramolecular and enzymatic reactions. 2. A theoretical study of the formation of transition states in cyclic anhydride formation

Journal of the American Chemical Society

Volumn 119, Issue 39, 1997, Pages 9103-9113

  Lightstone, Felice C ^a   Bruice, Thomas C ^a  

^a UNIVERSITY OF CALIFORNIA   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

ACID ANHYDRIDE;

ARTICLE; CALCULATION; CYCLIZATION; DRUG STRUCTURE; ENTHALPY; ENTROPY; GAS; MOLECULAR DYNAMICS; THEORETICAL STUDY; THERMODYNAMICS;

EID: 0030870598     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja970982g     Document Type: Article

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17. Because AM1/SM2.1 was parameterized to reproduce the experimental solvation free energies, AM1/SM2.1 solvation calculations were also performed on the gas phase HF/6-31+G(d) geometries. The calculated free energies of solvation were added to the gas phase HF/6-31+G(d) electronic energy. These AM1/SM2.1 solvated energies show that the HMC of I is slightly lower in energy than its extended structure (Table 7). For II, the UMC is ∼3 kcal/mol lower in energy than its extended structure. Because we anticipated that experimentally in water the extended structure should be lower in energy than the IIMC, the AM1/SM2.1 solvation estimation does not seem to be a good method for this system.