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Conformations, protonation sites, and metal complexation of benzohydroxamic acid. A theoretical and experimental study

AuthorsGarcía, Begoña ; Ibeas, S.; Leal, J. M.; Secco, F.; Venturini, M.; Senent, María Luisa ; Niño, A.; Muñoz, Concepción
Issue Date2005
PublisherAmerican Chemical Society
CitationInorganic Chemistry 44: 2908-2919 (2005)
AbstractA theoretical and experimental study on the structure and deprotonation of benzohydroxamic acid (BHA) has been performed. Calculations at the RHF/cc-pVDZ level, refined by the B3LYP/AUG-cc-pVDZ method, indicate that, in the gas phase, Z amide is the most stable structure of both neutral and deprotonated BHA. 1H-1H nuclear Overhauser enhancement spectroscopy and 1H-1H correlation spectroscopy spectra in acetone, interpreted with ab initio interatomic distances, reveal that BHA is split into the Z and E forms, the [E]/[Z] ratio being 75:25 at -80°C. The formation of E-E, Z-Z, and E-Z dimers has been detected; in the presence of water, the dimers dissociate to the corresponding monomers. The rates of proton exchange within the Z and E forms and between E and Z were measured by dynamic 1H NMR in the -60 to 40°C temperature range; an increase in water content lowers the rate of exchange of the E isomer. The effect of D2O on the NMR signals indicates a fast hydrogen exchange between D2O and the E and Z amide forms. The sequence of the acid strength at low temperatures is (N)HE ≈ (O)HE < (O)HZ ≈ (N)H Z. The kinetics of complex formation between BHA and Ni2+, investigated by the stopped-flow method, show that both neutral BHA and its anion can bind Ni2+. Whereas the anion reacts at a >normal> speed, the rate of water replacement from Ni(H2O)6 2+ by neutral BHA is about 1 order of magnitude less than expected. This behavior was interpreted assuming that, in aqueous solution, BHA mainly adopts a closed (hydrogen-bonded) Z configuration, which should open (with an energy penalty) for the metal binding process to occur. © 2005 American Chemical Society.
Identifiersdoi: 10.1021/ic049438g
issn: 0020-1669
Appears in Collections:(CFMAC-IEM) Artículos
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