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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
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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
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84906367806
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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
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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.
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84906396443
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PO is the length (in angstroms) of the bond in question.
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PO is the length (in angstroms) of the bond in question.
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53
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84906382143
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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
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55
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54
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0037174379
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Cheng, H.; Nikolic-Hughes, I.; Wang, J. H.; Deng, H.; O'Brien, P. J.; Wu, L.; Zhang, Z. Y.; Herschlag, D.; Callender, R. J. Am. Chem. Soc. 2002, 124, 11295-11306.
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57
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84906396442
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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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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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