[en] Molecular electrostatic potential was used as a criterion of extraction ability of a series of neutral organophosphorus compounds: trimethylphosphate-trimethylphosphonate-trimethylphosphinate-trimethylphosphine oxide- and for analyzing mechanism of acid hydrolysis of alkylphosphates. Charge distribution in P=0 fragment was calculated by MNDO, CNDO/2 (sp), CNDO/2 (spa) methods. It was shown that negative charge on oxygen of phosphoryl group decreased from the first member of mentioned extractant series to the last one, while the extraction ability in this series increased. NMR data showed that changes in the electronic structure of tributhylphosphate (TBP) in complexes with Zr, Hf and Sc nitrates were similar to ones, observed in TBP complexes with HNO₃, but were more pronounced. Strond effect of cations of these metals on TBP electronic structure was considered to be the reason of their catalytic activity during acid hydrolysis of this extractant