Influence of Branching on the Conformational Space: Case Study of Tri- sec-butyl Phosphate Using Matrix Isolation Infrared Spectroscopy and DFT Computations.

Abstract

The conformational analysis of long chain phosphates poses a serious challenge due to the presence of rotationally flexible multiple alkyl groups. Tri- sec-butyl phosphate (TsBP) is an interesting example, in which branching can be expected to influence the conformational landscape. To solve the conformational problem of TsBP systematically, the conformations of model dimethyl- sec-butyl phosphate (DMsBP), a molecule possessing a single secondary butyl strand, were analyzed. On the basis of the analysis of the energy profile of DMsBP, a few conformational bunches were eliminated. The presence of branched methyl group appears to completely influence the conformational space of TsBP and as a result, the number of conformations is drastically reduced in comparison to its structural isomer, tri- n-butyl phosphate (TBP). B3LYP level of theory in association with 6-311++G(d,p) basis set was used for computing all the conformer geometries. Experimentally, the conformations of TsBP were studied using infrared spectroscopy by trapping the molecule in N2 and Ar matrixes at low temperatures, which were correlated well with the computational results.