Synthesis, Spectroscopic characterization and Theoretical calculations of ClF2CC(O)N=PCl3 ([chloro(difluor)acetyl]phosphorimidic trichloride)

ANA G. IRIARTE; EDGARDO H. CUTIN; GUSTAVO A. ARGÜELLO

SPECTROCHIMICA ACTA. PART A, MOLECULAR AND BIOMOLECULAR SPECTROSCOPY.

PERGAMON-ELSEVIER SCIENCE LTD

Lugar: Amsterdam; Año: 2013 vol. 120 p. 137 - 143

1386-1425

The synthesis of [chloro(difluor)acetyl]phosphorimidic trichloride (ClF2CC(O)N=PCl3), together with a tentative assignment of the Vibrational, NMR and mass spectra, are reported. Quantum chemical calculations (MP2 and B3LYP methods with 6-311+G(d) and 6-311+G(2df,p) basis sets) predict three stable conformers in the gas phase (syn, gauche and anti, defined according to the rotation around both the Cl-C-C-N and the C-C-N-P dihedral angles). However, only a single C1 symmetry conformer is observed in the liquid phase, possessing the C=O double bond in synperiplanar orientation with respect to the P=N double bond, and the Cl-C bond distorted from the plane defined by the CC(O)NP entity. A Natural bond orbital (NBO) analysis was carried out for the title compound and related molecules in order to provide an explanation about the electronic properties.