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</o:shapelayout></xml><![endif]--></head><body lang=SL link=blue vlink=purple><div class=WordSection1><p class=MsoTitle align=left style='margin:0cm;margin-bottom:.0001pt;text-align:left'><span style='font-size:18.0pt;font-family:"Verdana","sans-serif";color:black;font-weight:normal'>VABILO NA PREGLOV KOLOKVIJ / INVITATION TO THE PREGL COLLOQUIUM<o:p></o:p></span></p><p class=MsoNormal><b><span style='font-size:12.0pt;font-family:"Verdana","sans-serif"'><o:p> </o:p></span></b></p><p class=MsoNormal style='text-autospace:none'><b><span style='font-size:24.0pt;font-family:"Verdana","sans-serif";mso-fareast-language:SL'>Prof. Dr. Peter R. Schreiner<o:p></o:p></span></b></p><p class=MsoNormal style='text-autospace:none'><span lang=FR style='font-family:"Verdana","sans-serif"'>Institute of Organic Chemistry, Justus-Liebig University, Heinrich-Buff-Ring 58, Giessen, Germany<o:p></o:p></span></p><p class=MsoNormal><b><span style='font-size:11.0pt;font-family:"Verdana","sans-serif"'><o:p> </o:p></span></b></p><p class=MsoNormal><b><span style='font-family:"Verdana","sans-serif"'><o:p> </o:p></span></b></p><p class=MsoNormal style='line-height:150%'><b><span style='font-size:16.0pt;line-height:150%;font-family:"Verdana","sans-serif"'>Četrtek / Thursday, 16. 02. 2012, ob / at 13:00<o:p></o:p></span></b></p><h6 align=left style='mso-margin-top-alt:0cm;margin-right:0cm;margin-bottom:6.0pt;margin-left:0cm;text-align:left'><span lang=FR style='font-size:11.0pt;font-family:"Verdana","sans-serif"'>Velika predavalnica Kemijskega inštituta / Lecture Hall at the National Institute of Chemistry<o:p></o:p></span></h6><p class=MsoNormal style='text-autospace:none'><b><span lang=EN-GB style='font-size:8.0pt;font-family:"Verdana","sans-serif";color:#993366'><o:p> </o:p></span></b></p><p class=MsoNormal style='text-autospace:none'><b><span lang=EN-GB style='font-size:24.0pt;font-family:"Verdana","sans-serif";color:#993366'>Tunneling Control of Chemical Reactions<sup>[1]</sup><o:p></o:p></span></b></p><p class=MsoNormal><span lang=EN-GB style='font-size:11.0pt;font-family:"Garamond","serif";mso-fareast-language:EN-GB'><o:p> </o:p></span></p><p class=MsoNormal><span lang=EN-GB style='font-size:11.0pt;font-family:"Garamond","serif";mso-fareast-language:EN-GB'>Abstract:<o:p></o:p></span></p><p class=ZingAbstractText align=left style='margin-bottom:6.0pt;text-align:left'><span lang=EN-GB style='font-size:11.0pt;font-family:"Garamond","serif"'>Chemical reactivity is traditionally understood<sup>[<a href="#_ENREF_2" title="Eyring, 1935 #19793"><span style='color:windowtext;text-decoration:none'>2</span></a>, <a href="#_ENREF_3" title="Evans, 1935 #19796"><span style='color:windowtext;text-decoration:none'>3</span></a>]</sup> in terms of kinetic versus thermodynamic control,<sup>[<a href="#_ENREF_4" title="Woodward, 1944 #19797"><span style='color:windowtext;text-decoration:none'>4</span></a>, <a href="#_ENREF_5" title="Catchpole, 1944 #19798"><span style='color:windowtext;text-decoration:none'>5</span></a>]</sup> wherein the driving force is the lowest activation barrier among the possible reaction paths or the lowest free energy of the final products, respectively. Here we expose quantum mechanical tunneling as a third driving force that can overwrite traditional kinetic control and govern reactivity based on nonclassical penetration of the potential energy barriers connecting the reactants and products. These findings are exemplified with the first experimental isolation and full spectroscopic and theoretical characterization of the elusive hydroxycarbenes (R–C–OH, <b>1</b>)<sup>[<a href="#_ENREF_6" title="Gerbig, 2010 #19801"><span style='color:windowtext;text-decoration:none'>6-9</span></a>]</sup> that undergo facile [1,2]hydrogen tunneling to the corresponding aldehydes under barriers of nearly 30.0 kcal mol<sup>–1</sup> with half-lives of around 1–2 h even at experimental temperatures as low as 10 K, despite of the presence of paths with substantially lower barriers (e.g., CH-tunneling in <b>1b</b> to <b>3</b> or rearrangement of <b>1c</b> to <b>4</b>). We will demonstrate that this is a general phenomenon,<sup>[<a href="#_ENREF_10" title="Gerbig, 2011 #23707"><span style='color:windowtext;text-decoration:none'>10</span></a>, <a href="#_ENREF_11" title="Ley, 2011 #23814"><span style='color:windowtext;text-decoration:none'>11</span></a>]</sup> as exemplified by other OH-tunneling examples such as the rotational isomerization of monomeric benzoic acid.<sup>[<a href="#_ENREF_12" title="Amiri, 2010 #20053"><span style='color:windowtext;text-decoration:none'>12</span></a>]</sup> Such tunneling processes do not merely represent corrections to the reaction rate, they <i>are</i> the reaction rate, i.e., the completely <i>control</i> the reaction outome.<sup>[<a href="#_ENREF_1" title="Schreiner, 2011 #24258"><span style='color:windowtext;text-decoration:none'>1</span></a>]</sup></span><span lang=EN-GB style='font-size:12.0pt;font-family:"Garamond","serif"'><o:p></o:p></span></p><p class=MsoNormal><b><span style='font-size:12.0pt;font-family:"Garamond","serif";mso-fareast-language:SL'><img border=0 width=400 height=152 id="Picture_x0020_2" src="cid:image001.png@01CCE7E6.5B71C9E0"></span></b><b><span lang=FR style='font-size:12.0pt;font-family:"Garamond","serif";mso-fareast-language:EN-GB'><o:p></o:p></span></b></p><p class=MsoNormal><b><span lang=FR style='font-size:12.0pt;font-family:"Garamond","serif";mso-fareast-language:EN-GB'><o:p> </o:p></span></b></p><p class=MsoNormal><b><span lang=FR style='font-size:12.0pt;font-family:"Garamond","serif";mso-fareast-language:EN-GB'>–––––––––<o:p></o:p></span></b></p><p class=MsoNormal style='margin-left:36.0pt;text-indent:-36.0pt'><a name="_ENREF_1"><span lang=FR style='font-family:"Garamond","serif"'>[1] P. R. Schreiner, H. P. Reisenauer, D. Ley, D. Gerbig, C.-H. Wu, W. D. Allen, <i>Science </i><b>2011</b>, <i>332</i>, 1300.</span></a><span lang=FR style='font-family:"Garamond","serif"'><o:p></o:p></span></p><p class=MsoNormal style='margin-left:36.0pt;text-indent:-36.0pt'><a name="_ENREF_2"><span lang=FR style='font-family:"Garamond","serif"'>[2] H. Eyring, <i>J. Chem. Phys. </i><b>1935</b>, <i>3</i>, 107.</span></a><span lang=FR style='font-family:"Garamond","serif"'><o:p></o:p></span></p><p class=MsoNormal style='margin-left:36.0pt;text-indent:-36.0pt'><a name="_ENREF_3"><span lang=FR style='font-family:"Garamond","serif"'>[3] M. G. Evans, M. Polanyi, <i>Trans. Faraday Soc. </i><b>1935</b>, <i>31</i>, 875.</span></a><span lang=FR style='font-family:"Garamond","serif"'><o:p></o:p></span></p><p class=MsoNormal style='margin-left:36.0pt;text-indent:-36.0pt'><a name="_ENREF_4"><span lang=FR style='font-family:"Garamond","serif"'>[4] R. B. Woodward, H. Baer, <i>J. Am. Chem. Soc. </i><b>1944</b>, <i>66</i>, 645.</span></a><span lang=FR style='font-family:"Garamond","serif"'><o:p></o:p></span></p><p class=MsoNormal style='margin-left:36.0pt;text-indent:-36.0pt'><a name="_ENREF_5"><span lang=FR style='font-family:"Garamond","serif"'>[5] A. G. Catchpole, E. D. Hughes, C. K. Ingold, <i>J. Chem. Soc. </i><b>1944</b>, <i>11</i>, 8.</span></a><span lang=FR style='font-family:"Garamond","serif"'><o:p></o:p></span></p><p class=MsoNormal style='margin-left:36.0pt;text-indent:-36.0pt'><a name="_ENREF_6"><span lang=FR style='font-family:"Garamond","serif"'>[6] D. Gerbig, H. P. Reisenauer, C.-H. Wu, D. Ley, W. D. Allen, P. R. Schreiner, <i>J. Am. Chem. Soc. </i><b>2010</b>, <i>132</i>, 7273.</span></a><span lang=FR style='font-family:"Garamond","serif"'><o:p></o:p></span></p><p class=MsoNormal style='margin-left:36.0pt;text-indent:-36.0pt'><a name="_ENREF_7"><span lang=FR style='font-family:"Garamond","serif"'>[7] D. Gerbig, D. Ley, H. P. Reisenauer, P. R. Schreiner, <i>Beilstein J. Org. Chem. </i><b>2010</b>, <i>6</i>, 1061.</span></a><span lang=FR style='font-family:"Garamond","serif"'><o:p></o:p></span></p><p class=MsoNormal style='margin-left:36.0pt;text-indent:-36.0pt'><a name="_ENREF_8"><span lang=FR style='font-family:"Garamond","serif"'>[8] P. R. Schreiner, H. P. Reisenauer, F. C. Pickard IV, A. C. Simmonett, W. D. Allen, E. Mátyus, A. G. Császár, <i>Nature </i><b>2008</b>, <i>453</i>, 906.</span></a><span lang=FR style='font-family:"Garamond","serif"'><o:p></o:p></span></p><p class=MsoNormal style='margin-left:36.0pt;text-indent:-36.0pt'><a name="_ENREF_9"><span lang=FR style='font-family:"Garamond","serif"'>[9] P. R. Schreiner, H. P. Reisenauer, <i>Angew. Chem. Int. Ed. </i><b>2008</b>, <i>47</i>, 7071.</span></a><span lang=FR style='font-family:"Garamond","serif"'><o:p></o:p></span></p><p class=MsoNormal style='margin-left:36.0pt;text-indent:-36.0pt'><a name="_ENREF_10"><span lang=FR style='font-family:"Garamond","serif"'>[10] D. Gerbig, D. Ley, P. R. Schreiner, <i>Org. Lett. </i><b>2011</b>, <i>13</i>, 3526.</span></a><span lang=FR style='font-family:"Garamond","serif"'><o:p></o:p></span></p><p class=MsoNormal style='margin-left:36.0pt;text-indent:-36.0pt'><a name="_ENREF_11"><span lang=FR style='font-family:"Garamond","serif"'>[11] D. Ley, D. Gerbig, J. P. Wagner, H. P. Reisenauer, P. R. Schreiner, <i>J. Am. Chem. Soc. </i><b>2011</b>, <i>133</i>, 13614.</span></a><span lang=FR style='font-family:"Garamond","serif"'><o:p></o:p></span></p><p class=MsoNormal style='margin-left:36.0pt;text-indent:-36.0pt'><a name="_ENREF_12"><span lang=FR style='font-family:"Garamond","serif"'>[12] S. Amiri, H. P. Reisenauer, P. R. Schreiner, <i>J. Am. Chem. Soc. </i><b>2010</b>, <i>132</i>, 15902.</span></a><span lang=FR style='font-family:"Garamond","serif"'><o:p></o:p></span></p><p class=MsoNormal style='line-height:150%'><span lang=EN-US style='font-size:8.0pt;line-height:150%;font-family:"Arial","sans-serif";mso-fareast-language:SL'><o:p> </o:p></span></p><p class=MsoNormal style='line-height:150%'><span lang=EN-US style='font-size:12.0pt;line-height:150%;font-family:"Arial","sans-serif";mso-fareast-language:SL'>Vljudno vabljeni! / Kindly invited!<o:p></o:p></span></p><p class=MsoNormal><span lang=FR style='font-size:11.0pt;font-family:"Calibri","sans-serif"'><o:p> </o:p></span></p><p class=MsoNormal><span lang=FR style='font-size:11.0pt;font-family:"Calibri","sans-serif"'><o:p> </o:p></span></p></div></body></html>