| Abstract: |
A yellow solid material [PxHy] has been obtained in the reaction of phosphine (PH3) and nitric oxide (NO) at room temperature, and characterized by TGA-MS and ATR-FTIR, along with the previous SEM and X-ray fluorescence spectroscopy. In this work using Complete Basis Set (CBS-QB3) methods, a plausible mechanism has been investigated for the phosphine polymerization in the presence of nitric oxide (NO). Theoretical explorations with the ab. initio method suggest: a) instead of the monomer, the nitric oxide dimer acts as an initial oxidant, b) the resulting phosphine oxides (H3P=O ↔ H3P+O−) in the gas phase draw each other via strong dipolar interactions between the P-O groups, c) consequently an auto-catalyzed polymerization occurs among the phosphine oxides, forming P-P chemical bonds and losing water. The possible structures of polyhydride phosphorus polymer were discussed. In the calculations, a series of cluster models were computed to simulate the polymerization. |
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