Experimental and Computational Studies of Carbonyl Diazide (CON6) as a Precursor to Diazirinone (CON2)

Details Experimental and Computational Studies of Carbonyl Diazide (CON6) as a Precursor to Diazirinone (CON2) Experimental and Computational Studies of Carbonyl Diazide (CON6) as a Precursor to Diazirinone (CON2)

Oct 2011

adsabs.harvard.edu/cgi-bin/nph-data_query?bibcode=2011mwac.meet..t04e&link_type=abstract

Midwest Astrochemistry Meeting 2011, held 21-22 October at the University of Illinois at Urbana-Champaign. http://midwest.astroc

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Intrigued by the reported 2005 synthesis of diazirinone (1), we carried out further experimental and theoretical studies aimed at the detailed matrix-isolation and millimeter-wave spectroscopic characterizations of 1. Diazirinone (1) is a peculiar isoconjugate of two very stable molecules and may be of astrochemical interest. Unfortunately, the original reported methods of diazirinone (1) generation did not yield this species, rather its decomposition products. Inspired by a more recent gas phase pyrolysis of CON6 (2) to yield CON2 (1), we proposed a new method of generating CON6 (2) in solution as a precursor of diazirinone (1). This new synthesis may allow us to generate larger quantities of both CON6 and CON2 for investigation by millimeter-wave spectroscopy.
We are able to safely generate carbonyl diazide (2) in sufficient yield from the reaction of triphosgene (3) and tetrabutylammonium azide in diethyl ether. This has allowed us to obtain both matrix-isolation and gas phase IR spectra of carbonyl diazide (2). After purification, it has a gas-phase lifetime that allows samples to be useable for up to several weeks. However, it is a shock-sensitive material that must be handled with care to prevent violent decomposition.
In order to provide better mechanistic insight into the decomposition of carbonyl diazide (2) to diazirinone (1), we have engaged in a DFT and ab initio computational study. We have found a pathway between the two species via the triplet acylnitrene, CON4, and an oxaziridine CON2 species, but not at sufficiently low energies to allow for the trapping and detection of diazirinone (1). Preliminary millimeter-wave spectra have been obtained from several synthesized and purified samples of CON6 (2). However, the assignment of the spectra lines has been unexpectedly problematic. We have placed several CON6 (2) samples, confirmed by IR spectroscopy at the time of sample loading, into our instrument and obtained two different sets of rotational lines. This rotational puzzle will be investigated further with a significantly upgraded millimeter-wave spectrometer.

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