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Volumn 112, Issue 10, 2008, Pages 3217-3221

Theoretical study of specific hydrogen-bonding effects on the bridging P-OR bond strength of phosphate monoester dianions

Author keywords

[No Author keywords available]

Indexed keywords

HYDROGEN;

EID: 42449129225     PISSN: 15206106     EISSN: None     Source Type: Journal    
DOI: 10.1021/jp710945w     Document Type: Article
Times cited : (11)

References (57)
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    • Sinnot, M. L, Ed, Academic Press: London
    • Hengge, A. C. In Comprehensive Biological Catalysis; Sinnot, M. L., Ed.; Academic Press: London, 1998; Vol. 1, pp 517-542.
    • (1998) Comprehensive Biological Catalysis , vol.1 , pp. 517-542
    • Hengge, A.C.1
  • 14
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    • We use the word associative to indicate that the sum of the bonding between the incoming nucleophile and outgoing leaving group is greater than the corresponding sum of bond orders in the reactants or products. Thus, in associative transition states, there is greater formation of bond order to the nucleophile than loss of bond order to the leaving group (i.e, bond order increases in going from the ground state to the transition state, Conversely, dissociative transition states are those in which die sum of nucleophile and leaving group bond orders is less than the corresponding bond orders in the reactants or products i.e, bond order decreases in going from the ground state to the transition state
    • We use the word "associative" to indicate that the sum of the bonding between the incoming nucleophile and outgoing leaving group is greater than the corresponding sum of bond orders in the reactants or products. Thus, in associative transition states, there is greater formation of bond order to the nucleophile than loss of bond order to the leaving group (i.e., bond order increases in going from the ground state to the transition state). Conversely, dissociative transition states are those in which die sum of nucleophile and leaving group bond orders is less than the corresponding bond orders in the reactants or products (i.e., bond order decreases in going from the ground state to the transition state).
  • 19
    • 0029015718 scopus 로고
    • Zhang, Z. J. Biol. Chem. 1995, 270, 11199-11204.
    • (1995) J. Biol. Chem , vol.270 , pp. 11199-11204
    • Zhang, Z.1
  • 25
    • 84906410875 scopus 로고    scopus 로고
    • This intuitively more reasonable alternative has been proposed on the basis of computational studies using the empirical valence bond approach. 26-29 According to these studies, the reaction proceeds through an associative phosphorane-like transition state and requires a net charge of -2 in the Michaelis complex in conflict with the net charge of -3 inferred from experimental data.18,21-24 Other computational studies, however, have yielded conclusions in complete agreement with the protonation states shown in Scheme I.30-32
    • 30-32
  • 35
    • 84906367805 scopus 로고    scopus 로고
    • Frisch, M. J, Trucks, G. W, Schlegel, H. B, Scuseria, G. E, Robb, M. A, Cheeseman, J. R, Zakrzewski, V. G, Montgomery, J. A, Jr, Stratmann, R. E, Burant, J. C, Dapprich, S, Millam, J. M, Daniels, A. D, Kudin, K. N, Strain, M. C, Farkas, O, Tomasi, J, Barone, V, Cossi, M, Cammi, R, Mennucci, B, Pomelli, C, Adamo, C, Clifford, S, Ochterski, J, Petersson, G. A, Ayala, P. Y, Cui, Q, Morokuma, K, Malick, D. K, Rabuck, A. D, Raghavachari, K, Foresman, J. B, Cioslowski, J, Ortiz, J. V, Stefanov, B. B, Liu, G, Liashenko, A, Piskorz, P, Komaromi, I, Gomperts, R, Martin, R. L, Fox, D. J, Keith, T, Al-Laham, M. A, Peng, C. Y, Nanayakkara, A, Gonzalez, C, Challacombe, M, Gill, P. M. W, Johnson, B. G, Chen, W, Wong, M. W, Andres, J. L, Head-Gordon, M, Replogle, E. S, Pople, J. A. Gaussian 98, revision A.11; Gaussian, Inc, Pittsburgh, PA, 1998
    • Frisch, M. J.; Trucks, G. W.; Schlegel, H. B.; Scuseria, G. E.; Robb, M. A.; Cheeseman, J. R.; Zakrzewski, V. G.; Montgomery, J. A., Jr.; Stratmann, R. E.; Burant, J. C.; Dapprich, S.; Millam, J. M.; Daniels, A. D.; Kudin, K. N.; Strain, M. C.; Farkas, O.; Tomasi, J.; Barone, V.; Cossi, M.; Cammi, R.; Mennucci, B.; Pomelli, C.; Adamo, C.; Clifford, S.; Ochterski, J.; Petersson, G. A.; Ayala, P. Y.; Cui, Q.; Morokuma, K.; Malick, D. K.; Rabuck, A. D.; Raghavachari, K.; Foresman, J. B.; Cioslowski, J.; Ortiz, J. V.; Stefanov, B. B.; Liu, G.; Liashenko, A.; Piskorz, P.; Komaromi, I.; Gomperts, R.; Martin, R. L.; Fox, D. J.; Keith, T.; Al-Laham, M. A.; Peng, C. Y.; Nanayakkara, A.; Gonzalez, C.; Challacombe, M.; Gill, P. M. W.; Johnson, B. G.; Chen, W.; Wong, M. W.; Andres, J. L.; Head-Gordon, M.; Replogle, E. S.; Pople, J. A. Gaussian 98, revision A.11; Gaussian, Inc.: Pittsburgh, PA, 1998.
  • 36
  • 45
    • 84906367806 scopus 로고    scopus 로고
    • Pseudopotentials were used to allow future comparisons with previous studies and incoming work in which biologically relevant metal ions will be included in the reacting system
    • Pseudopotentials were used to allow future comparisons with previous studies and incoming work in which biologically relevant metal ions will be included in the reacting system.
  • 50
    • 84906396443 scopus 로고    scopus 로고
    • PO is the length (in angstroms) of the bond in question.
    • PO is the length (in angstroms) of the bond in question.
  • 53
    • 84906382143 scopus 로고    scopus 로고
    • Previous results inferred from a vibrational spectroscopy study in solution indicate that a similar bond lengthening occurs in alkyl phosphate esters when the alcohol substituents vary in pKa by ∼12 units.54 In contrast to the X-ray51 and computational 52 data, a recent study using 18O isotopic shifts in 31P NMR to monitor the bond order of P-O bonds in solution found that the P-OR bond was largely unaffected by the electronic nature (alkyl versus aryl) of the R moiety.55
    • 55
  • 57
    • 84906396442 scopus 로고    scopus 로고
    • 51 between the activation free energy for the unimolecular heterolysis of P-OR bonds of phosphate monoester dianions and their bond lengths as observed in crystal structures (longer bonds being more reactive).
    • 51 between the activation free energy for the unimolecular heterolysis of P-OR bonds of phosphate monoester dianions and their bond lengths as observed in crystal structures (longer bonds being more reactive).


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