Geometry-Tunable Lewis Acidity of Amidinium Cations and Its Relevance to Redox Reactions of the Thauer Metal-Free Hydrogenase: A Theoretical Study

Angewandte Chemie (International Edition in English)

Volumn 36, Issue 1-2, 1997, Pages 107-109

  Cioslowski, Jerzy ^a   Boche, Gernot ^b  

^a FLORIDA STATE UNIVERSITY   (United States)

^b PHILIPPS UNIVERSITY MARBURG   (Germany)

Author keywords

Carbocations; Enzymes; Hydrogenases; Thermodynamics

Indexed keywords

EID: 0030793322     PISSN: 05700833     EISSN: None     Source Type: Journal    
DOI: 10.1002/anie.199701071     Document Type: Article

References (30)

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24. -1 (the present calculations). For a recent comparison of the high-accuracy G1, G2, G2MP2, and CBS-4 methods see: J. W. Ochterski, G. A. Petersson, K. B. Wiberg, J. Am. Chem. Soc. 1995, 117, 11299-11308.
25. The solvent effects were modeled with the SCI-PCM (Self-Consistent Isodensity Polarized Continuum Model) formulism using the dielectric constant of 80 and the default isodensity value. All geometries were fully optimized in the presence of the reaction field of the solvent. The calculations were carried out with the GAUSSIAN 94 suite of programs; GAUSSIAN 94; M. J. Frisch, G. W. Trucks, H. B. Schlegel, P. M. W. Gill, B. G. Johnson, M. A. Robb, J. R. Cheeseman, T. Keith, G. A. Petersson, J. A. Montgomery, K. Raghavachari, M. A. Al-Laham, V. G. Zakrzewski, J. V. Ortiz, J. B. Foresman, J. Cioslowski, B. B. Stefanov, A. Nanayakkara, M. Challacombe, C. Y. Peng, P. Y. Ayala, W. Chen, M. W. Wong, J. L. Andres, E. S. Replogle, R. Gomperts, R. L. Martin, D. J. Fox, J. S. Binkley, D. J. Defrecs, J. Baker, J. P. Stewart, M. Head-Gordon, C. Gonzalez, J. A. Pople, Gaussian, Inc., Pittsburgh, PA, 1995.
26. +.
27. + has been given by J. A. Gerlt, P. G. Gassman, Biochemistry, 1993, 32, 11 943-11952; see also G. L. Kenyon, J. A. Gerlt, G. A. Petsko, J. W. Kozarich, Acc. Chem. Res. 1995, 28, 178-180, and the references therein.
28. + has been given by J. A. Gerlt, P. G. Gassman, Biochemistry, 1993, 32, 11 943-11952; see also G. L. Kenyon, J. A. Gerlt, G. A. Petsko, J. W. Kozarich, Acc. Chem. Res. 1995, 28, 178-180, and the references therein.
29. -1. Setting ΔE(φ) = 0 produces the value quoted in the text.
30. 3) might also be of interest in considerations concerning the transition state of the reaction of this hydrogenase.