Journal
CHEMISTRY-A EUROPEAN JOURNAL
Volume 21, Issue 3, Pages 1073-1080Publisher
WILEY-V C H VERLAG GMBH
DOI: 10.1002/chem.201404271
Keywords
ab initio calculations; organophosphorus compounds; photoelectron spectroscopy; radicals; thermochemistry
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Funding
- Swiss Federal Office for Energy (BFE) [101969/152433]
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The production of phosphoryl species (PO, PO2, HOPO) is believed to be of great importance for efficient flame-retardant action in the gas phase. We present a detailed investigation of the thermal decomposition of dimethyl methylphosphonate (DMMP) probed by vacuum ultraviolet (VUV) synchrotron radiation and imaging photoelectron photoion coincidence (iPEPICO) spectroscopy. This technique provides a snapshot of the thermolysis process and direct evidence of how the reactive phosphoryl species are generated during heat exposure. One of the key findings of this work is that only PO is formed in high concentration upon DMMP decomposition, whereas PO2 is absent. It can be concluded that the formation of PO2 needs an oxidative environment, which is typically the case in a real flame. Based on the identification of products such as methanol, formaldehyde, and PO, as well as the intermediates OPCH3, H2CPOH, and H2CP(O)H, supported by quantum chemical calculations, we were able to describe the predominant pathways that lead to active phosphoryl species during the thermal decomposition of DMMP.
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