Intramolecular general acid catalysis of the hydrolysis of 2-(2'-imidazolium)phenyl phosphate, and bond length-reactivity correlations for reactions of phosphate monoester monoanions.
Rate constants for the hydrolysis of 2-(2'-imidazolium)phenyl hydrogen phosphate (IMPP) in water at pH<6 indicate that activation by the imidazolium moiety disappears with the deprotonation of the phosphate group, and the reaction involves the hydrogen-bonding of the imidazolium NH with the aryl oxygen leaving group. The reaction should involve a near-planar conformation of the imidazolium and the phenyl groups in the activated complex, which favors proton-transfer. The crystal structure of IMPP was solved, and a bond length-reactivity correlation for reactions of phosphate monoester monoanions is described.
Brandão
Tiago A S
TA
Departamento de Química, Universidade Federal de Santa Catarina, Florianópolis, SC 88040-900, Brazil.
Orth
Elisa S
ES
Rocha
Willian R
WR
Bortoluzzi
Adailton J
AJ
Bunton
Clifford A
CA
Nome
Faruk
F
D000143:Acids / Q000737:chemistry*; D002384:Catalysis; D003198:Computer Simulation; D018360:Crystallography, X-Ray; D004952:Esters / Q000737:chemistry*; D006859:Hydrogen / Q000737:chemistry; D006863:Hydrogen-Ion Concentration; D006868:Hydrolysis; D007093:Imidazoles / Q000737:chemistry*; D007700:Kinetics; D008958:Models, Molecular; D015394:Molecular Structure; D009943:Organophosphorus Compounds / Q000737:chemistry*; D013696:Temperature; D017186:Titrimetry
C520708:2-(2'-imidazolium)phenyl phosphate; D000143:Acids; D004952:Esters; D007093:Imidazoles; D009943:Organophosphorus Compounds; D006859:Hydrogen