{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,9,10]],"date-time":"2026-09-10T15:15:18Z","timestamp":1789053318150,"version":"build-2803163510"},"reference-count":68,"publisher":"Wiley","issue":"23","license":[{"start":{"date-parts":[[2017,4,5]],"date-time":"2017-04-05T00:00:00Z","timestamp":1491350400000},"content-version":"vor","delay-in-days":0,"URL":"http:\/\/onlinelibrary.wiley.com\/termsAndConditions#vor"}],"funder":[{"name":"Swiss Federal Office for Energy","award":["SI\/501269-01"],"award-info":[{"award-number":["SI\/501269-01"]}]}],"content-domain":{"domain":[],"crossmark-restriction":false},"short-container-title":["Chemistry A European J"],"published-print":{"date-parts":[[2017,4,24]]},"abstract":"<jats:title>Abstract<\/jats:title>\n                  <jats:p>\n                    The thermal behavior of organophosphorus compounds is intricate and poorly understood but crucial for understanding gas\u2010phase flame inhibition, syntheses of thermally active phosphorus\u2010based reactive precursors, catalytic combustion, incineration of toxic nerve gases, and astrochemistry. In this work, the pyrolysis of dimethyl phosphoramidate was investigated using photoion photoelectron coincidence spectroscopy in combination with vacuum ultraviolet synchrotron radiation. This technique enables isomer\u2010selective detection of reactive intermediates, which are crucial in the understanding of the decomposition process. Combined with quantum chemical calculations, the experimental results permit the formulation of a comprehensive pyrolysis reaction pathway for dimethyl phosphoramidate, consisting of several reactive phosphorus species on four possible decomposition pathways. Compared to the decomposition of dimethyl methyl phosphonate, which leads exclusively to the formation of PO radicals, substitution of the methyl with an amino group most notably yields phosphorus nitride (P\u2261N). This mostly favored reaction pathway involves the subsequent loss of methanol and formaldehyde to yield three PONH\n                    <jats:sub>2<\/jats:sub>\n                    tautomers, which eliminate water to generate P\u2261N. The thermally induced production of PN species and its possible role in flame inhibition has not previously been reported. In addition, the adiabatic ionization energy of O=P(OCH\n                    <jats:sub>3<\/jats:sub>\n                    )\n                    <jats:sub>2<\/jats:sub>\n                    NH\n                    <jats:sub>2<\/jats:sub>\n                    was determined to be 9.79\u00b10.02\u2005eV.\n                  <\/jats:p>","DOI":"10.1002\/chem.201700402","type":"journal-article","created":{"date-parts":[[2017,4,5]],"date-time":"2017-04-05T14:12:54Z","timestamp":1491401574000},"page":"5595-5601","source":"Crossref","is-referenced-by-count":31,"title":["Probing Phosphorus Nitride (P\u2261N) and Other Elusive Species Formed upon Pyrolysis of Dimethyl Phosphoramidate"],"prefix":"10.1002","volume":"23","author":[{"ORCID":"https:\/\/orcid.org\/0000-0002-7154-1520","authenticated-orcid":false,"given":"Shuyu","family":"Liang","sequence":"first","affiliation":[{"name":"Laboratory of Inorganic Chemistry ETH Z\u00fcrich, Swiss Federal Institute of Technology  Vladimir-Prelog-Weg 1-5\/10 8093 Z\u00fcrich Switzerland"},{"name":"Additives and Chemistry, Advanced Fibers Empa, Swiss Federal Laboratories for Materials Science  Lerchenfeldstrasse 5 9014 St. Gallen Switzerland"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-1251-4549","authenticated-orcid":false,"given":"Patrick","family":"Hemberger","sequence":"additional","affiliation":[{"name":"Laboratory for Femtochemistry and Synchrotron Radiation Paul Scherrer Institute  WSLA\/115 5232 Villigen-PSI Switzerland"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-3146-0176","authenticated-orcid":false,"given":"Jo\u00eblle","family":"Levalois\u2010Gr\u00fctzmacher","sequence":"additional","affiliation":[{"name":"Laboratory of Inorganic Chemistry ETH Z\u00fcrich, Swiss Federal Institute of Technology  Vladimir-Prelog-Weg 1-5\/10 8093 Z\u00fcrich Switzerland"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-1531-8906","authenticated-orcid":false,"given":"Hansj\u00f6rg","family":"Gr\u00fctzmacher","sequence":"additional","affiliation":[{"name":"Laboratory of Inorganic Chemistry ETH Z\u00fcrich, Swiss Federal Institute of Technology  Vladimir-Prelog-Weg 1-5\/10 8093 Z\u00fcrich Switzerland"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-9891-5249","authenticated-orcid":false,"given":"Sabyasachi","family":"Gaan","sequence":"additional","affiliation":[{"name":"Additives and Chemistry, Advanced Fibers Empa, Swiss Federal Laboratories for Materials Science  Lerchenfeldstrasse 5 9014 St. Gallen Switzerland"}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"311","published-online":{"date-parts":[[2017,4,5]]},"reference":[{"key":"e_1_2_7_1_1","unstructured":"\u00a0"},{"key":"e_1_2_7_2_2","doi-asserted-by":"publisher","DOI":"10.1126\/science.aaa1495"},{"key":"e_1_2_7_3_2","first-page":"16","volume-title":"Pyrolysis of Carbohydrates, Vol. 28","author":"Moldoveanu S. 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