Formation of the N-Iodopyridinium Cation in an Alkane Environment: Mid-Infrared Linear Dichroism Investigation of the Pyridine-Iodine System in Stretched Polyethylene

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Abstract

It is well known that pyridine (py) and iodine (I2) form a 1:1 molecular complex, py-I2. Within the framework of a student project at Roskilde University [1], we have recently investigated the formation and mid-infrared linear dichroism of the complex in a stretched polyethylene (PE) matrix. However, the observed spectra displayed not only the expected transitions due to py and py-I2, but also a third, prominent series of sharp transitions, evidently due to one or more additional products. On the basis of a comparison with literature spectra, we assigned these transitions to the N-iodopyridinium cation (pyI+). This assignment is consistent with the observed polarization data. Ionic side reactions (py-I2 = pyI+ + I–, py-I2 + I2 = pyI+ + I3–, etc.) are easily observed in binary pyridine-iodine mictures and in polar solvents, but not so easily in non-polar media. We are thus surprised to see the apparent efficiency with which the pyI+ cation is formed in an apolar and aprotic medium like PE. With excess iodine, the peaks assigned to pyI+ dominate the observed mid-infrared spectrum. We suspect that a driving force for the ionic reaction is the formation of polyiodide anions in the channels of the polymer medium. Further investigation of the phenomenon is in progress. [1] H. S. van Deurs, M. L. M. Espersen, R. Nissen, M. H. Rasmussen, C. J. S. Schönbeck, Student Project, Roskilde University, June 2006 (in Danish).
Original languageEnglish
Title of host publicationXVIII International Conference on Physical Organic Chemistry : ICPOC-18, August 20-25, 2006
EditorsM. K. Cyranski, K. Wozniak, T. M. Krygowski
Number of pages2
PublisherInternational Union of Pure and Applied Chemistry
Publication date2006
Pages42-43
ISBN (Print)83-89585-11-1
Publication statusPublished - 2006
EventInternational Conference on Physical Organic Chemistry (ICPOC) - Warszawa, Poland
Duration: 20 Aug 200625 Aug 2006
Conference number: 18

Conference

ConferenceInternational Conference on Physical Organic Chemistry (ICPOC)
Number18
CountryPoland
CityWarszawa
Period20/08/200625/08/2006

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