Phosphorous bonding in PCl3:H2O adducts: A matrix isolation infrared and ab initio computational studies

Non-covalent interaction between PCl3 and H2O was studied using matrix isolation infrared spectroscopy and ab initio computations. Computations indicated that the adducts are stabilized through novel P center dot center dot center dot O type phosphorus bonding and conventional P-CI center dot center dot center dot H type hydrogen bonding interactions, where the former adduct is the global minimum. Experimentally, the P center dot center dot center dot O phosphorus bonded adduct was identified in N-2 matrix, which was evidenced from the shifts in the vibrational wavenumbers of the modes involving PCl3 and H2O sub-molecules. Atoms in Molecules and Natural Bond Orbital analyses have been performed to understand the nature of interactions in the phosphorus and hydrogen bonded adducts. Interestingly, experimental evidence for the formation of higher PCl3H2O adduct was also observed in N-2 matrix. (C) 2016 Elsevier Inc. All rights reserved.