How does the OH group affect the conversion of carbonyl oxide to dioxirane?

Makaleler > Tam Makale · 2000

Yazarlar: Cenk SELÇUKİ, Viktorya Aviyente

JOURNAL OF MOLECULAR STRUCTURE-THEOCHEM, SCI Expanded İndekslerine Giren Dergi, Uluslararası, 2000, cilt 530, ss 97-107

DOI: 10.1016/s0166-1280(00)00330-4

Özet

<p><span style="color: rgb(46, 46, 46); font-family: NexusSerif, Georgia, &quot;Times New Roman&quot;, Times, STIXGeneral, &quot;Cambria Math&quot;, &quot;Lucida Sans Unicode&quot;, &quot;Microsoft Sans Serif&quot;, &quot;Segoe UI Symbol&quot;, &quot;Arial Unicode MS&quot;, serif; font-size: 18px;">The effects of the hydroxy group on the conversion of carbonyl oxide to dioxirane have been examined in the gas phase and in solution with B3LYP/6-31G(d,p). The solvent has been modeled with the SCIPCM method. All the possible orientations of the hydroxy group (</span><em style="margin: 0px; padding: 0px; color: rgb(46, 46, 46); font-family: NexusSerif, Georgia, &quot;Times New Roman&quot;, Times, STIXGeneral, &quot;Cambria Math&quot;, &quot;Lucida Sans Unicode&quot;, &quot;Microsoft Sans Serif&quot;, &quot;Segoe UI Symbol&quot;, &quot;Arial Unicode MS&quot;, serif; font-size: 18px;">syn</em><span style="color: rgb(46, 46, 46); font-family: NexusSerif, Georgia, &quot;Times New Roman&quot;, Times, STIXGeneral, &quot;Cambria Math&quot;, &quot;Lucida Sans Unicode&quot;, &quot;Microsoft Sans Serif&quot;, &quot;Segoe UI Symbol&quot;, &quot;Arial Unicode MS&quot;, serif; font-size: 18px;">-in,&nbsp;</span><em style="margin: 0px; padding: 0px; color: rgb(46, 46, 46); font-family: NexusSerif, Georgia, &quot;Times New Roman&quot;, Times, STIXGeneral, &quot;Cambria Math&quot;, &quot;Lucida Sans Unicode&quot;, &quot;Microsoft Sans Serif&quot;, &quot;Segoe UI Symbol&quot;, &quot;Arial Unicode MS&quot;, serif; font-size: 18px;">syn</em><span style="color: rgb(46, 46, 46); font-family: NexusSerif, Georgia, &quot;Times New Roman&quot;, Times, STIXGeneral, &quot;Cambria Math&quot;, &quot;Lucida Sans Unicode&quot;, &quot;Microsoft Sans Serif&quot;, &quot;Segoe UI Symbol&quot;, &quot;Arial Unicode MS&quot;, serif; font-size: 18px;">-out,&nbsp;</span><em style="margin: 0px; padding: 0px; color: rgb(46, 46, 46); font-family: NexusSerif, Georgia, &quot;Times New Roman&quot;, Times, STIXGeneral, &quot;Cambria Math&quot;, &quot;Lucida Sans Unicode&quot;, &quot;Microsoft Sans Serif&quot;, &quot;Segoe UI Symbol&quot;, &quot;Arial Unicode MS&quot;, serif; font-size: 18px;">anti</em><span style="color: rgb(46, 46, 46); font-family: NexusSerif, Georgia, &quot;Times New Roman&quot;, Times, STIXGeneral, &quot;Cambria Math&quot;, &quot;Lucida Sans Unicode&quot;, &quot;Microsoft Sans Serif&quot;, &quot;Segoe UI Symbol&quot;, &quot;Arial Unicode MS&quot;, serif; font-size: 18px;">-in,&nbsp;</span><em style="margin: 0px; padding: 0px; color: rgb(46, 46, 46); font-family: NexusSerif, Georgia, &quot;Times New Roman&quot;, Times, STIXGeneral, &quot;Cambria Math&quot;, &quot;Lucida Sans Unicode&quot;, &quot;Microsoft Sans Serif&quot;, &quot;Segoe UI Symbol&quot;, &quot;Arial Unicode MS&quot;, serif; font-size: 18px;">anti</em><span style="color: rgb(46, 46, 46); font-family: NexusSerif, Georgia, &quot;Times New Roman&quot;, Times, STIXGeneral, &quot;Cambria Math&quot;, &quot;Lucida Sans Unicode&quot;, &quot;Microsoft Sans Serif&quot;, &quot;Segoe UI Symbol&quot;, &quot;Arial Unicode MS&quot;, serif; font-size: 18px;">-out) on carbonyl oxide and dioxirane (in, out) have been considered. The&nbsp;</span><span style="margin: 0px; padding: 0px; font-weight: bolder; color: rgb(46, 46, 46); font-family: NexusSerif, Georgia, &quot;Times New Roman&quot;, Times, STIXGeneral, &quot;Cambria Math&quot;, &quot;Lucida Sans Unicode&quot;, &quot;Microsoft Sans Serif&quot;, &quot;Segoe UI Symbol&quot;, &quot;Arial Unicode MS&quot;, serif; font-size: 18px;">S</span><span style="margin: 0px; padding: 0px; font-size: 13.5px; line-height: 0; position: relative; vertical-align: baseline; bottom: -0.25em; color: rgb(46, 46, 46); font-family: NexusSerif, Georgia, &quot;Times New Roman&quot;, Times, STIXGeneral, &quot;Cambria Math&quot;, &quot;Lucida Sans Unicode&quot;, &quot;Microsoft Sans Serif&quot;, &quot;Segoe UI Symbol&quot;, &quot;Arial Unicode MS&quot;, serif;"><span style="margin: 0px; padding: 0px; font-weight: bolder;">i</span></span><span style="color: rgb(46, 46, 46); font-family: NexusSerif, Georgia, &quot;Times New Roman&quot;, Times, STIXGeneral, &quot;Cambria Math&quot;, &quot;Lucida Sans Unicode&quot;, &quot;Microsoft Sans Serif&quot;, &quot;Segoe UI Symbol&quot;, &quot;Arial Unicode MS&quot;, serif; font-size: 18px;">&nbsp;(</span><em style="margin: 0px; padding: 0px; color: rgb(46, 46, 46); font-family: NexusSerif, Georgia, &quot;Times New Roman&quot;, Times, STIXGeneral, &quot;Cambria Math&quot;, &quot;Lucida Sans Unicode&quot;, &quot;Microsoft Sans Serif&quot;, &quot;Segoe UI Symbol&quot;, &quot;Arial Unicode MS&quot;, serif; font-size: 18px;">syn</em><span style="color: rgb(46, 46, 46); font-family: NexusSerif, Georgia, &quot;Times New Roman&quot;, Times, STIXGeneral, &quot;Cambria Math&quot;, &quot;Lucida Sans Unicode&quot;, &quot;Microsoft Sans Serif&quot;, &quot;Segoe UI Symbol&quot;, &quot;Arial Unicode MS&quot;, serif; font-size: 18px;">-in) conformer of hydroxy carbonyl oxide was not located as a stationary structure, instead peroxyformic acid is formed. The isomerization barrier for&nbsp;</span><span style="margin: 0px; padding: 0px; font-weight: bolder; color: rgb(46, 46, 46); font-family: NexusSerif, Georgia, &quot;Times New Roman&quot;, Times, STIXGeneral, &quot;Cambria Math&quot;, &quot;Lucida Sans Unicode&quot;, &quot;Microsoft Sans Serif&quot;, &quot;Segoe UI Symbol&quot;, &quot;Arial Unicode MS&quot;, serif; font-size: 18px;">S</span><span style="margin: 0px; padding: 0px; font-size: 13.5px; line-height: 0; position: relative; vertical-align: baseline; bottom: -0.25em; color: rgb(46, 46, 46); font-family: NexusSerif, Georgia, &quot;Times New Roman&quot;, Times, STIXGeneral, &quot;Cambria Math&quot;, &quot;Lucida Sans Unicode&quot;, &quot;Microsoft Sans Serif&quot;, &quot;Segoe UI Symbol&quot;, &quot;Arial Unicode MS&quot;, serif;"><span style="margin: 0px; padding: 0px; font-weight: bolder;">o</span></span><span style="color: rgb(46, 46, 46); font-family: NexusSerif, Georgia, &quot;Times New Roman&quot;, Times, STIXGeneral, &quot;Cambria Math&quot;, &quot;Lucida Sans Unicode&quot;, &quot;Microsoft Sans Serif&quot;, &quot;Segoe UI Symbol&quot;, &quot;Arial Unicode MS&quot;, serif; font-size: 18px;">&nbsp;is found to be twice as large as the one for the&nbsp;</span><span style="margin: 0px; padding: 0px; font-weight: bolder; color: rgb(46, 46, 46); font-family: NexusSerif, Georgia, &quot;Times New Roman&quot;, Times, STIXGeneral, &quot;Cambria Math&quot;, &quot;Lucida Sans Unicode&quot;, &quot;Microsoft Sans Serif&quot;, &quot;Segoe UI Symbol&quot;, &quot;Arial Unicode MS&quot;, serif; font-size: 18px;">A</span><span style="margin: 0px; padding: 0px; font-size: 13.5px; line-height: 0; position: relative; vertical-align: baseline; bottom: -0.25em; color: rgb(46, 46, 46); font-family: NexusSerif, Georgia, &quot;Times New Roman&quot;, Times, STIXGeneral, &quot;Cambria Math&quot;, &quot;Lucida Sans Unicode&quot;, &quot;Microsoft Sans Serif&quot;, &quot;Segoe UI Symbol&quot;, &quot;Arial Unicode MS&quot;, serif;"><span style="margin: 0px; padding: 0px; font-weight: bolder;">o</span></span><span style="color: rgb(46, 46, 46); font-family: NexusSerif, Georgia, &quot;Times New Roman&quot;, Times, STIXGeneral, &quot;Cambria Math&quot;, &quot;Lucida Sans Unicode&quot;, &quot;Microsoft Sans Serif&quot;, &quot;Segoe UI Symbol&quot;, &quot;Arial Unicode MS&quot;, serif; font-size: 18px;">&nbsp;and&nbsp;</span><span style="margin: 0px; padding: 0px; font-weight: bolder; color: rgb(46, 46, 46); font-family: NexusSerif, Georgia, &quot;Times New Roman&quot;, Times, STIXGeneral, &quot;Cambria Math&quot;, &quot;Lucida Sans Unicode&quot;, &quot;Microsoft Sans Serif&quot;, &quot;Segoe UI Symbol&quot;, &quot;Arial Unicode MS&quot;, serif; font-size: 18px;">A</span><span style="margin: 0px; padding: 0px; font-size: 13.5px; line-height: 0; position: relative; vertical-align: baseline; bottom: -0.25em; color: rgb(46, 46, 46); font-family: NexusSerif, Georgia, &quot;Times New Roman&quot;, Times, STIXGeneral, &quot;Cambria Math&quot;, &quot;Lucida Sans Unicode&quot;, &quot;Microsoft Sans Serif&quot;, &quot;Segoe UI Symbol&quot;, &quot;Arial Unicode MS&quot;, serif;"><span style="margin: 0px; padding: 0px; font-weight: bolder;">i</span></span><span style="color: rgb(46, 46, 46); font-family: NexusSerif, Georgia, &quot;Times New Roman&quot;, Times, STIXGeneral, &quot;Cambria Math&quot;, &quot;Lucida Sans Unicode&quot;, &quot;Microsoft Sans Serif&quot;, &quot;Segoe UI Symbol&quot;, &quot;Arial Unicode MS&quot;, serif; font-size: 18px;">&nbsp;in vacuum and in a polar media (</span><em style="margin: 0px; padding: 0px; color: rgb(46, 46, 46); font-family: NexusSerif, Georgia, &quot;Times New Roman&quot;, Times, STIXGeneral, &quot;Cambria Math&quot;, &quot;Lucida Sans Unicode&quot;, &quot;Microsoft Sans Serif&quot;, &quot;Segoe UI Symbol&quot;, &quot;Arial Unicode MS&quot;, serif; font-size: 18px;">?</em><span style="color: rgb(46, 46, 46); font-family: NexusSerif, Georgia, &quot;Times New Roman&quot;, Times, STIXGeneral, &quot;Cambria Math&quot;, &quot;Lucida Sans Unicode&quot;, &quot;Microsoft Sans Serif&quot;, &quot;Segoe UI Symbol&quot;, &quot;Arial Unicode MS&quot;, serif; font-size: 18px;">=78.5). Single point calculations with B3LYP/6-311+G(3df,2p)//B3LYP/6-31G(d,p) mimic the same trend.</span><br></p>

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