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Geometrical, conformational and spectroscopical properties of three chalcogenphosphates were studied comparatively. Rotational isomerism and conformational flexibility were evaluated for trimethyl phosphate, O,O,O-trimethyl thiophosphate and O,O,O-trimethyl selenophosphate by studying the vibrational and NMR spectroscopy. Semi empirical and ab initio calculations have been carried out. Experimental and theoretical results show similar conformational behavior, founding equivalent symmetries for conformations of minimal energies, but a decrease in the conformational flexibility is observed when going from O, to S and to Se species. This result would represent a new factor to explain the higher ability of interaction of O-organophosphorus compounds in some biological active sites, in esterases for example, with respect to the analogous S-organophosphorus compounds and Se-organophosphorus compounds.
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