PUMA publications for /user/theochem/IR%20chemie%20rauhuthttps://puma.ub.uni-stuttgart.de/user/theochem/IR%20chemie%20rauhutPUMA RSS feed for /user/theochem/IR%20chemie%20rauhut2024-03-28T17:38:43+01:00Photolysis of Carbonyl Diisocyanate: Generation of Isocyanatocarbonyl Nitrene and Diazomethanonehttps://puma.ub.uni-stuttgart.de/bibtex/25fc6d7f69f85235f80b08ed5aeda6c10/theochemtheochem2019-02-15T17:47:57+01:00chemie from:alexanderdenzel rauhut IR theoretische stuttgart spectroscopy,matrices,nitrenes,photochemistry,reactive theochem intermediates <span data-person-type="author" class="authorEditorList "><span><span itemtype="http://schema.org/Person" itemscope="itemscope" itemprop="author"><a title="Qifan Liu" itemprop="url" href="/person/1abe212a0ec512afe05899e6d160674a3/author/0"><span itemprop="name">Q. Liu</span></a></span>, </span><span><span itemtype="http://schema.org/Person" itemscope="itemscope" itemprop="author"><a title="Hongmin Li" itemprop="url" href="/person/1abe212a0ec512afe05899e6d160674a3/author/1"><span itemprop="name">H. Li</span></a></span>, </span><span><span itemtype="http://schema.org/Person" itemscope="itemscope" itemprop="author"><a title="Zhuang Wu" itemprop="url" href="/person/1abe212a0ec512afe05899e6d160674a3/author/2"><span itemprop="name">Z. Wu</span></a></span>, </span><span><span itemtype="http://schema.org/Person" itemscope="itemscope" itemprop="author"><a title="Dingqing Li" itemprop="url" href="/person/1abe212a0ec512afe05899e6d160674a3/author/3"><span itemprop="name">D. Li</span></a></span>, </span><span><span itemtype="http://schema.org/Person" itemscope="itemscope" itemprop="author"><a title="Helmut Beckers" itemprop="url" href="/person/1abe212a0ec512afe05899e6d160674a3/author/4"><span itemprop="name">H. Beckers</span></a></span>, </span><span><span itemtype="http://schema.org/Person" itemscope="itemscope" itemprop="author"><a title="Guntram Rauhut" itemprop="url" href="/person/1abe212a0ec512afe05899e6d160674a3/author/5"><span itemprop="name">G. Rauhut</span></a></span>, </span> and <span><span itemtype="http://schema.org/Person" itemscope="itemscope" itemprop="author"><a title="Xiaoqing Zeng" itemprop="url" href="/person/1abe212a0ec512afe05899e6d160674a3/author/6"><span itemprop="name">X. Zeng</span></a></span></span>. </span><span class="additional-entrytype-information"><span itemtype="http://schema.org/PublicationIssue" itemscope="itemscope" itemprop="isPartOf"><em><span itemprop="journal">Chem. - An Asian J.</span>, </em> <em><span itemtype="http://schema.org/PublicationVolume" itemscope="itemscope" itemprop="isPartOf"><span itemprop="volumeNumber">11 </span></span>(<span itemprop="issueNumber">20</span>):
<span itemprop="pagination">2953–2959</span></em> </span>(<em><span>2016<meta content="2016" itemprop="datePublished"/></span></em>)</span>Fri Feb 15 17:47:57 CET 2019Chem. - An Asian J.202953–2959{Photolysis of Carbonyl Diisocyanate: Generation of Isocyanatocarbonyl Nitrene and Diazomethanone}112016chemie from:alexanderdenzel rauhut IR theoretische stuttgart spectroscopy,matrices,nitrenes,photochemistry,reactive theochem intermediates {\textcopyright} 2016 Wiley-VCH Verlag GmbH {\&} Co. KGaA, Weinheim The stepwise decomposition of carbonyl diisocyanate, OC(NCO) 2 , has been studied by using IR spectroscopy in solid argon matrices at 16 K. Upon irradiation with an ArF laser ($\lambda$=193 nm), carbonyl diisocyanate split off CO and furnished a new carbonyl nitrene, OCNC(O)N, in its triplet ground state. Two conformers of the nitrene, syn and anti, that were derived from the two conformers of OC(NCO) 2 (62 {\%} syn–syn and 38 {\%} syn–anti) were identified and characterized by combining IR spectroscopy and quantum chemical calculations. Subsequent irradiation with visible light ($\lambda$ {\textgreater} 395 nm) caused the Curtius rearrangement of the nitrene into OCNNCO. In addition to the expected decomposition products, N 2 and CO, further photolysis of OCNNCO with the ArF laser yielded NOCN, through a diazomethanone (NNCO) intermediate. To further validate our proposed reaction mechanism, ArF-laser photolysis of the closely related NNNNCO and cyclo-N 2 CO in solid argon matrices were also studied. The observations of NOCN and in situ CO-trapped product OCNNCO provided indirect evidence to support the initial generation of NNCO as a common intermediate during the laser photolysis of OCNNCO, NNNNCO, and cyclo-N 2 CO.