Theoretical study of the structural, spectroscopic and energetic properties of difluoro(germylthio)phosphine and difluoro(germylseleno)phosphine in the gas phase

Theoretical methods have been employed to investigate the structural, spectroscopic and energetic properties of difluoro(germylthio)phosphine in the C-s symmetry in the gas phase. The levels of theory used are MP2 and DFT/B3LYP and the basis Set used for all atoms is 6-311G(d,p). The computed structural parameters, namely, bond lengths and bond angles and spectroscopic parameters, namely, infrared frequencies, Raman activities and NMR chemical shifts have been compared with experimental data reported in literature. The structure of this compound has been analysed using natural bond orbital approach. Both the ab initio methods perform satisfactorily when the predicted and experimental parameters are compared. We have extended this study, using the same methods and basis set, to the selenium analogue, namely, difluoro(germylseleno)phosphine for which literature is elusive. The MP2/6-311G(d,p) geometrical parameters for difluoro(germylseleno)phosphine are: r(P-Se) = 2.270, r(Ge-Se) = 2.386, r(P-F) = 1.604, r(Ge-H) = 1.530 angstrom, angle(Ge-Se-P) = 91.4, angle(F-P-F) = 96.7, angle(Se-P-F) = 99.9 and angle(Se-Ge-H) = 109.5 degrees. Apart from these, we have also studied the energetic parameters for their synthesis. The results indicate that formation of the sulphur-containing compound is favoured thermodynamically. (C) 2009 Elsevier Ltd. All rights reserved.