<html>  <head> <meta http-equiv="Content-Type" content="text/html; charset=windows-1252"> <meta name="GENERATOR" content="Microsoft FrontPage 4.0"> <meta name="ProgId" content="FrontPage.Editor.Document"> <title>Eric ROSE</title> </head>  <body bgcolor="#FFFFCC"> <table border="0" cellpadding="0" width="100%">   <tr>     <td width="22%" align="center"><span style="mso-bidi-font-size: 10.0pt; mso-bidi-font-weight: normal"><font size="1" color="#000000"><b style="mso-bidi-font-weight: normal; mso-bidi-font-size: 10.0pt"><a href="#1" name="0"> COMPLEXES ARENES-METAUX</a></b></font></span></td>     <td width="18%" align="center"><span style="mso-bidi-font-size: 10.0pt; mso-bidi-font-weight: normal"><font size="1" color="#000000"><b><a href="#2"> PORPHYRINES</a></b></font></span></td>     <td width="20%" align="center"><span lang="EN-GB" style="mso-bidi-font-size: 10.0pt; mso-ansi-language: EN-GB; mso-bidi-font-weight: normal"><font size="1" color="#000000"><a href="#3"> <span style="mso-bidi-font-size: 10.0pt; mso-ansi-language: EN-GB; mso-bidi-font-weight: normal"><b>7</b></span></a></font></span><b style="mso-bidi-font-weight: normal; mso-bidi-font-size: 10.0pt"><span lang="EN-GB" style="mso-bidi-font-size: 10.0pt; mso-ansi-language: EN-GB; mso-bidi-font-weight: normal"><font size="1" color="#000000"><a href="#3">        PUBLICATIONS SIGNIFICATIVES</a></font></span></b></td>     <td width="20%" align="center"><b style="mso-bidi-font-weight: normal; mso-bidi-font-size: 10.0pt"><span style="mso-bidi-font-size: 10.0pt; mso-bidi-font-weight: normal"><font size="1" color="#000000"><a href="#4">   COLLABORATIONS NATIONALES</a></font></span></b></td>     <td width="20%" align="center"><b style="mso-bidi-font-weight: normal; mso-bidi-font-size: 10.0pt"><span style="mso-bidi-font-size: 10.0pt; mso-bidi-font-weight: normal"><font size="1" color="#000000"><a href="#5">   COLLABORATIONS INTERNATIONALES</a></font></span></b></td>   </tr> </table> <p style="margin-top: 0">&nbsp;</p> <table border="0" cellspacing="0" cellpadding="0" style="border-collapse: collapse; mso-table-layout-alt: fixed; mso-padding-alt: 0cm 3.5pt 0cm 3.5pt" width="726">   <tr>     <td width="394" valign="top" style="padding-left: 3.5pt; padding-right: 3.5pt; padding-top: 0cm; padding-bottom: 0cm">       <p class="MsoNormal" align="right"><b style="mso-bidi-font-weight: normal">Eric       ROSE</b></p>       <p class="MsoNormal" align="right" style="text-indent: 0; margin: 0"><b style="mso-bidi-font-weight:normal">Directeur       de Recherche&nbsp;au CNRS DR1</b>: </p>       <p class="MsoNormal" align="right" style="text-indent: 0; margin: 0">&nbsp;</p>       <p class="MsoNormal" align="left">Stage Postdoctoral&nbsp;: Sjour de       longue dure  ltranger de 09/1975  09/1977 dans le Laboratoire       du Pr. J. Collman, Stanford University, CA, USA</p>       <p class="MsoNormal" align="left">Dtach au centre de Recherche       Roussel-Uclaf  Romainville, 102 Route de Noisy, BP9, 93230       (10/1977-06/1978)</p>       <p class="MsoNormal" align="left">Visiting scholar  l'Universit de       Stanford, CA, (USA) en 1986, 88, 92 et 96</p>       <p class="MsoNormal" align="left">Professeur associ  l'Universit de       Milan (Italie) en 2000,  l'Universit de Bonn (Allemagne) en 2001</p>       <p class="MsoNormal" align="left">Contrats OTAN avec l'Universit de       Stanford (USA) 1996-98,</p>     </td>     <td width="312" valign="top" style="padding-left: 3.5pt; padding-right: 3.5pt; padding-top: 0cm; padding-bottom: 0cm">       <p class="MsoNormal" align="left"><img src="rose.h2.jpg" v:shapes="_x0000_i1025" width="257" height="193" align="right"></p>       <p class="MsoNormal" align="left">&nbsp;</p>       <p class="MsoNormal" align="left">&nbsp;</p>       <p class="MsoNormal" align="left">&nbsp;</p>       <p class="MsoNormal" align="left">&nbsp;</p>       <p class="MsoNormal" align="left">&nbsp;</p>       <p class="MsoNormal" align="left">&nbsp;</p>       <p class="MsoNormal" align="left">&nbsp;</p>       <p class="MsoNormal" align="center">110 publications</p>       <p class="MsoNormal" align="center">70 confrences nationales et       internationales</p>       <p class="MsoNormal" align="center">88 communications</p>     </td>   </tr> </table> <p class="MsoNormal" align="center">&nbsp;Tlphone&nbsp;: 33 (0) 1 44 27 62 35</p> <p class="MsoNormal" align="center" style="text-align:center">Email&nbsp;: <a href="mailto:rose@ccr.jussieu.fr">rose@ccr.jussieu.fr</a></p> <p class="MsoNormal">&nbsp;</p> <p class="MsoNormal"><span style="font-size:14.0pt;mso-bidi-font-size: 10.0pt"><b style="mso-bidi-font-weight:normal"><a name="1"></a></b></span><b><font size="4">I) LES COMPLEXES ARENES-METAUX</font></b></p> <p class="MsoNormal">&nbsp;<u>1) La ractivit des arnes-tricarbonylchrome</u></p> <p class="MsoNormal" align="center"><span style="font-size:12.0pt;mso-bidi-font-size:10.0pt; font-family:Times;mso-fareast-font-family:Times;mso-bidi-font-family:&quot;Times New Roman&quot;; mso-ansi-language:FR;mso-fareast-language:FR;mso-bidi-language:AR-SA"><img src="rose.h1.gif" v:shapes="_x0000_i1025" width="605" height="115"></span></p> <p style="margin-left: 80">: dcouverte de trois nouvelles ractions sans antcdent en Chimie Organomtallique: <b style="mso-bidi-font-weight:normal">les substitutions nuclophiles aromatiques S<span style="mso-text-raise:-2.0pt">N</span>Ar <i style="mso-bidi-font-style:normal">cine</i>, <i style="mso-bidi-font-style: normal">tl-mta</i> et <i style="mso-bidi-font-style:normal">tl-para</i></b> qui <b style="mso-bidi-font-weight:normal">permettent d'introduire un substituant en <i style="mso-bidi-font-style:normal">ortho</i>, en <i style="mso-bidi-font-style:normal">mta</i> ou en <i style="mso-bidi-font-style: normal">para</i> d'un groupe partant</b>. L'ide au dpart consistait  utiliser un complexe substitu par un bon groupe partant X et  traiter le milieu ractionnel par un nuclophile NuLi puis par un acide pour liminer HX afin de raromatiser le cycle, ce qui constitue la force motrice de la raction. <p class="MsoNormal" align="center" style="text-align: center"><img border="0" src="rose.h12.gif" width="488" height="115"></p> <p style="margin-left: 80">L'exemple suivant illustre la substitution <i style="mso-bidi-font-style:normal">tl-mta</i>: le nuclophile s'est fix en <i style="mso-bidi-font-style:normal">mta</i> du groupe partant OPh. Le point fort de ces ractions est quelles se font <b style="mso-bidi-font-weight:normal">sans perte de lentit Cr(CO)<sub>3</sub>.</b> <p class="MsoNormal" style="text-align: justify; line-height: 18.0pt; margin-left: 80"><b style="mso-bidi-font-weight:normal">Pourquoi est-ce important&nbsp;?</b></p> <p class="MsoNormal" style="text-align: justify; margin-left: 80"><span style="mso-spacerun: yes">&nbsp;</span>Cela permet maintenant d'une part de fonctionnaliser facilement un arne et ce, <b style="mso-bidi-font-weight: normal">rgioslectivement</b>, sur un cycle aromatique et d'atteindre des structures difficiles d'accs par les voies classiques de la chimie organique et d'autre part de transformer Cr(CO)<span style="mso-text-raise:-2.0pt">3</span> complex sur le cycle en le rcuprant sous forme de Cr(CO)<span style="mso-text-raise:-2.0pt">6</span> en prsence de CO (brevet). Cr(CO)<span style="mso-text-raise:-2.0pt">6</span> par coordination aux arnes est ncessaire  la prparation des complexes de dpart. Le mcanisme intime de ces ractions a t dtermin et fait intervenir des hydrures de chrome et des isomrisations de dines<span style="mso-spacerun: yes">&nbsp; </span>(<i style="mso-bidi-font-style:normal">Coord. Chem. Rev.</i>, 1998). Nous appliquons actuellement ces ractions en utilisant des complexes chiraux que nous savions prparer facilement (<i style="mso-bidi-font-style:normal">J. Am. Chem. Soc.</i>, 1992 et 1993) afin d'accder  des composs organiques chiraux susceptibles d'avoir des proprits pouvant intresser les entreprises pharmaceutiques. Nous gnralisons actuellement ces ractions aux complexes du Mn et du Fe.</p> <p class="MsoNormal" style="text-align: justify; line-height: 150%; margin-left: 80; margin-top: 0cm; margin-bottom: .0001pt">&nbsp;</p> <p class="MsoNormal" style="margin-top:0cm;margin-right:-9.25pt;margin-bottom: 0cm;margin-left:-1.0pt;margin-bottom:.0001pt;text-align:justify;line-height: 150%"><u>2) La ractivit des arnes tricarbonylmanganse</u></p> <p class="MsoNormal" style="margin-top:0cm;margin-right:-9.25pt;margin-bottom: 0cm;margin-left:-1.0pt;margin-bottom:.0001pt;text-align:justify;line-height: 150%">&nbsp;</p> <p class="MsoNormal" style="text-align: justify; margin-left: 80"><u>:</u> dcouverte de deux nouvelles ractions sans antcdent en Chimie Organomtallique du Mn, les substitutions nuclophiles <i style="mso-bidi-font-style:normal">cin</i> et <i style="mso-bidi-font-style:normal">tl</i>. L'ide tait de savoir si on pouvait dcouvrir des ractions analogues avec des complexes d'hapticits autres qu<span style="font-family:Symbol">h</span><span style="mso-text-raise: 3.0pt">6</span>. Est-ce qu'un complexe <span style="font-family:Symbol">h</span><span style="mso-text-raise:3.0pt">5</span>-cyclohexadinyltricarbonylemanganse substitu par un groupe partant X peut liminer HX? L'exemple suivant illustre cette nouvelle raction.</p> <p class="MsoNormal" style="margin-top:0cm;margin-right:-9.25pt;margin-bottom: 0cm;margin-left:-1.0pt;margin-bottom:.0001pt;text-align:justify;line-height: 18.0pt">&nbsp;</p> <p class="MsoNormal" align="center"><img border="0" src="rose.h5.gif" v:shapes="_x0000_i1026" width="579" height="136"></p> <p class="MsoNormal" style="text-align: justify; margin-left: 80"><b style="mso-bidi-font-weight:normal">Pourquoi est-ce important&nbsp;?</b></p> <p class="MsoNormal" style="text-align: justify; margin-left: 80; margin-top: 0cm; margin-bottom: .0001pt">&nbsp;Cela permet d'accder au mcanisme intime de cette raction qui implique l'limination d'un hydrogne agostique et du groupe partant X (limination 1,5 de H et de X: <i style="mso-bidi-font-style:normal">Organometallics</i>, <b style="mso-bidi-font-weight:normal">1996</b>, <i style="mso-bidi-font-style: normal"><u>15</u></i>, 4373; <i style="mso-bidi-font-style:normal">Coord. <span lang="EN-GB" style="mso-ansi-language: EN-GB">Chem. Rev.</span></i><span lang="EN-GB" style="mso-ansi-language:EN-GB"> <b style="mso-bidi-font-weight:normal">1998</b>, <i style="mso-bidi-font-style: normal">Current Org. Chem. </i><b style="mso-bidi-font-weight:normal">1999</b>). </span>Ces ractions <i style="mso-bidi-font-style:normal">cine</i> et <i style="mso-bidi-font-style:normal">tele</i> sont donc gnrales en Chimie Organomtallique et permettent deffectuer des hydro-daminations, hydro-dchlorations, hydro-dsulfurations...</p> <p class="MsoNormal" style="text-align: justify; margin-left: 80; margin-top: 0cm; margin-bottom: .0001pt">&nbsp;</p> <p style="text-align: justify; margin-left: 80" class="MsoNormal"><b style="mso-bidi-font-weight: normal">Perspectives</b></p> <p class="MsoNormal" style="margin-left: 80">&nbsp;<b style="mso-bidi-font-weight:normal">: </b>suite  la synthse de complexes binuclaires, trinuclaires et polynuclaires du Cr, du Fe et du Mn avec des hapticits diffrentes et en collaboration avec cinq autres quipes europennes, nous avons obtenu un <b style="mso-bidi-font-weight:normal">rseau europen de quatre ans (Avril 1998, Avril 2002)</b> qui nous permet de continuer ce sujet porteur relatif  la synthse de <b style="mso-bidi-font-weight: normal">nouveaux matriaux</b> dont certains sont actuellement tudis en optique non linaire. Succinctement, nous avons reli un complexe organomtallique cationique accepteur dlectrons <b style="mso-bidi-font-weight: normal">A</b>  un complexe organomtallique donneur dlectrons <b style="mso-bidi-font-weight:normal">D</b>, via un espaceur <b style="mso-bidi-font-weight: normal">E</b> capable de transfrer des lectrons (<i style="mso-bidi-font-style: normal">Eur. J. Inorg. Chem<b style="mso-bidi-font-weight:normal">. </b></i><b style="mso-bidi-font-weight:normal">1999</b> et <b style="mso-bidi-font-weight: normal">2000</b>).</p> <p class="MsoNormal" style="text-align: justify; line-height: 150%; margin-left: 80; margin-right: -9.25pt; margin-top: 0cm; margin-bottom: .0001pt">&nbsp;</p> <p class="MsoNormal" align="center" style="text-align: center"><img border="0" src="rose.h6.gif" v:shapes="_x0000_i1027" width="267" height="55"></p> <p class="MsoNormal" style="text-align: justify; margin-left: 80"><span style="background:white">Remarque&nbsp;: Jai volontairement t bref sur la partie organomtallique car les travaux rcents non publis rsultent<span style="mso-spacerun: yes">&nbsp; </span>dun travail dquipe et je ne peux les rendre publiques actuellement<b style="mso-bidi-font-weight:normal">. </b>Je me suis donc limit au principe.</span></p> <p class="MsoNormal" style="text-align: justify; margin-left: 80"><span style="background-color: white; background-repeat: repeat; background-attachment: scroll; background-position: 0%"><a href="../../recher/activite.htm">Pour des informations complmentaires</a>...</span></p> <p class="MsoNormal" style="line-height: 18.0pt; margin-left: -1.0pt; margin-right: -9.25pt; margin-top: 0cm; margin-bottom: .0001pt" align="center"><a href="#0"><img border="0" src="../../../../images/lacot.2.gif" width="17" height="28"></a></p> <p class="MsoNormal" style="line-height: 18.0pt; margin-left: -1.0pt; margin-right: -9.25pt; margin-top: 0cm; margin-bottom: .0001pt" align="center"><img border="0" src="../../../../images/espace.jpg" width="80%" height="1%"></p> <p class="MsoNormal"><span style="font-size: 14.0pt; mso-bidi-font-size: 10.0pt; mso-bidi-font-weight: normal"><a name="2"></a></span><b><font size="4">II) PORPHYRINES</font></b></p> <p class="MsoNormal" style="text-align: justify; line-height: 18.0pt; margin-left: 80; margin-right: -18.85pt">Synthse de nouvelles gnrations de porphyrines protges sur leurs <b style="mso-bidi-font-weight:normal">2 faces</b>  afin d'obtenir:</p> <p class="MsoNormal" style="text-align: justify; mso-list: l0 level1 lfo1; margin-left: 90">a)<span style="font:7.0pt &quot;Times New Roman&quot;">&nbsp;&nbsp;&nbsp;&nbsp;&nbsp; </span>de nouveaux <u>catalyseurs d'oxydation asymtrique</u></p> <p class="MsoNormal" style="text-align: justify; mso-list: l0 level1 lfo1; margin-left: 90">b)<span style="font:7.0pt &quot;Times New Roman&quot;">&nbsp;&nbsp;&nbsp;&nbsp;&nbsp; </span>de nouveaux <u>modles d'hmoprotines</u> (cyt P<span style="mso-text-raise:-2.0pt">450</span>, cyt c, cytochrome-c oxydase)</p> <p class="MsoNormal" style="margin-left: 80">&nbsp;</p> <div style="mso-element:frame;mso-element-frame-hspace:7.05pt;mso-element-wrap: around;mso-element-anchor-vertical:paragraph;mso-element-anchor-horizontal: page;mso-element-left:79.2pt;mso-element-top:13.05pt;mso-height-rule:exactly">   <table cellspacing="0" cellpadding="0" hspace="0" vspace="0" align="left">     <tr>       <td valign="top" align="left" style="padding-top:0cm;padding-right:7.05pt;   padding-bottom:0cm;padding-left:7.05pt">         <p class="MsoNormal" style="text-align: justify; background-color: #FFFFCA; background-repeat: repeat; background-attachment: scroll; mso-shading: windowtext; mso-pattern: gray-30 yellow; mso-element: frame; mso-element-frame-hspace: 7.05pt; mso-element-wrap: around; mso-element-anchor-vertical: paragraph; mso-element-anchor-horizontal: page; mso-element-left: 79.2pt; mso-element-top: 13.05pt; mso-height-rule: exactly; margin-left: 80; background-position: 0%"><b style="mso-bidi-font-weight:normal">Pourquoi         des porphyrines protges sur leurs deux faces?</b><span style="font-size:10.0pt">         </span></p>       </td>     </tr>   </table> </div> <p class="MsoNormal" style="margin-left: 80">&nbsp;</p> <p class="MsoNormal" style="margin-left: 80">&nbsp;Rappelons que les mtallo porphyrines du Fe(II) en prsence d'O<span style="mso-text-raise: -2.0pt">2</span> <b style="mso-bidi-font-weight:normal">1</b> sont connues pour donner instantanment des porphyrines face  face <span style="font-family: Symbol">m</span>-oxo <b style="mso-bidi-font-weight:normal">2</b>. Il y a oxydation irrversible du Fe(II) en Fe(III).</p> <p class="MsoNormal" align="center"><span style="mso-ignore:vglayout"><img border="0" src="rose.h13.gif" width="483" height="174"></span> <p style="margin-left: 80">&nbsp;Afin de rsoudre ce problme, nous nous sommes d'abord proposs de prparer des porphyrines protges sur leurs deux faces que nous avons appeles porphyrines &quot;gyroscope&quot; <b style="mso-bidi-font-weight:normal">3</b> et des porphyrines  anses de panier  deux anses chirales <b style="mso-bidi-font-weight: normal">4</b>. Nous avons obtenu le premier modle<span style="mso-spacerun: yes">&nbsp; </span><b style="mso-bidi-font-weight:normal">4-Fe-CO </b>qui fixe moins bien le monoxyde de carbone que la myoglobine elle-mme et le premier modle qui discrimine CO de O<sub>2</sub> dune manire semblable  celle de lhmoglobine. Nous voulons montrer maintenant que la fixation de CO seffectue difficilement dans le cas des hmoprotines naturelles  cause de la <b style="mso-bidi-font-weight:normal">dformation</b> du cycle porphyrinique (Inorg. Chem. <b style="mso-bidi-font-weight:normal">1998</b>, 37, 6532). Ayant acquis un savoir faire certain lors de ces synthses dlicates, nous nous sommes proposs de trouver une stratgie d'accs encore plus efficace  des porphyrines protges sur leurs deux faces. <p class="MsoNormal" align="center">&nbsp;<img border="0" src="rose.h8.gif" width="626" height="258"></p> <p class="MsoNormal" align="center" style="margin-top:0cm;margin-right:-9.25pt; margin-bottom:0cm;margin-left:-1.0pt;margin-bottom:.0001pt;text-align:center; line-height:18.0pt">&nbsp;</p> <p class="MsoNormal" style="text-align: justify; margin-left: 80">D'o l'ide simple de prparer des porphyrines de type <b style="mso-bidi-font-weight:normal">6</b> et ce, en grande quantit. La brique de base de notre synthse est laldhyde <b style="mso-bidi-font-weight:normal">5</b> dont la prparation a t ralise sur plusieurs centaines de grammes. Par condensation de cet aldhyde sur le pyrrole, nous avons isol la porphyrine <b style="mso-bidi-font-weight:normal">6a</b> (X=<span style="mso-text-raise:3.0pt">t</span>Bu, R=NO<span style="mso-text-raise:-2.0pt">2</span>) soluble dans les solvants organiques. Sachant qu'il est impossible d'obtenir une porphyrine octa-nitre par condensation de pyrrole sur le 2,6-dinitrobenzaldhyde, le fait de fonctionnaliser l'aldhyde par un groupe tertiobutyle nous a permis d'accder  plusieurs grammes de ces porphyrines octa-nitres, l'ide simple d'apporter quatre groupes tertiobutyles  une porphyrine pour la solubiliser, a permis <b style="mso-bidi-font-weight:normal">de dbloquer une situation qui tait compltement dans l'impasse</b> (<i style="mso-bidi-font-style:normal">J. Ar. Chem. Soc.,</i> <b style="mso-bidi-font-weight:normal">1996</b>, <i style="mso-bidi-font-style:normal">118</i>, 1567).</p> <p class="MsoNormal" align="center"><span style="mso-ignore:vglayout"><img border="0" src="rose.h14.gif" width="626" height="188"></span> <p style="margin-left: 80">La rduction des groupes nitro nous a donn les porphyrines octa-amines <b style="mso-bidi-font-weight:normal">6b</b> (X=<span style="mso-text-raise:3.0pt">t</span>Bu, R=NH<span style="mso-text-raise:-2.0pt">2</span>) sur lesquelles on peut condenser des chlorures d'acides chiraux afin d'obtenir par exemple la porphyrine <b style="mso-bidi-font-weight:normal">6c </b>(R=NHCOC*(CF<span style="mso-text-raise:-2.0pt">3</span>)(OMe)(C<span style="mso-text-raise:-2.0pt">6</span>H<span style="mso-text-raise:-2.0pt">5</span>) avec 8 piquets Mosher teste actuellement en tant que catalyseur d'oxydation asymtrique d'olfines et de liaisons C-H non actives. La condensation de huit chlorures d'acides conjugus donne l'octa-accepteur de Michael <b style="mso-bidi-font-weight:normal">6d</b> sur lequel peuvent ragir des amines, par exemple la ttramine suivante:{NH(CH<span style="mso-text-raise: -2.0pt">2</span>-CH<span style="mso-text-raise:-2.0pt">2</span>)}<span style="mso-text-raise:-2.0pt">4</span> qui conduit  la porphyrine &quot;tonneau&quot; <b style="mso-bidi-font-weight:normal">6e</b>. Grce  ces rsultats, nous sommes actuellement les pionniers dans le domaine fascinant des drivs des (2,6-diaminophnyl) porphyrines (<i style="mso-bidi-font-style: normal">Coord. </i><i style="mso-bidi-font-style:normal"><span lang="EN-GB" style="mso-ansi-language:EN-GB">Chem. Rev.</span></i><span lang="EN-GB" style="mso-ansi-language:EN-GB"> <b style="mso-bidi-font-weight:normal">1998</b>, 178-180, 1407&nbsp;; <i style="mso-bidi-font-style:normal">Polyhedron</i>, <b style="mso-bidi-font-weight:normal">2000</b>).<b style="mso-bidi-font-weight: normal"> </b></span>Nous venons dobtenir une structure radiocristallographique de <b style="mso-bidi-font-weight:normal">6d-Zn</b>. <p class="MsoNormal" align="center" style="text-align: center"><img border="0" src="rose.h10.gif" v:shapes="_x0000_i1028" width="497" height="472"></p> <p class="MsoNormal" style="text-align: justify; margin-left: 80; margin-right: -9.35pt">&nbsp;</p> <div style="mso-element:frame;mso-element-frame-hspace:7.05pt;mso-element-wrap: around;mso-element-anchor-vertical:paragraph;mso-element-anchor-horizontal: page;mso-element-left:64.8pt;mso-element-top:.5pt;mso-height-rule:exactly">   <table cellspacing="0" cellpadding="0" hspace="0" vspace="0" align="left">     <tr>       <td valign="top" align="left" style="padding-top:0cm;padding-right:7.05pt;   padding-bottom:0cm;padding-left:7.05pt">         <p class="MsoNormal" style="text-align: justify; background-color: #FFFFCA; background-repeat: repeat; background-attachment: scroll; mso-shading: windowtext; mso-pattern: gray-30 yellow; mso-element: frame; mso-element-frame-hspace: 7.05pt; mso-element-wrap: around; mso-element-anchor-vertical: paragraph; mso-element-anchor-horizontal: page; mso-element-left: 64.8pt; mso-element-top: .5pt; mso-height-rule: exactly; margin-left: 80; margin-right: -9.25pt; margin-top: 0cm; margin-bottom: .0001pt; background-position: 0%"><b style="mso-bidi-font-weight:normal">Pourquoi         est-ce important?</b><span style="font-size:10.0pt"> </span></p>       </td>     </tr>   </table> </div> <p class="MsoNormal" style="margin-top:0cm;margin-right:-9.25pt;margin-bottom: 0cm;margin-left:-1.0pt;margin-bottom:.0001pt;text-align:justify;line-height: 18.0pt">&nbsp;</p> <p class="MsoNormal" style="text-align: justify; line-height: 18.0pt; margin-left: 80; margin-top: 0cm; margin-bottom: .0001pt">&nbsp;</p> <p class="MsoNormal" style="text-align: justify; margin-left: 80">Cela permet d'obtenir rapidement en <b style="mso-bidi-font-weight:normal">TROIS</b> tapes une nouvelle gnration de porphyrines chirales protges sur leurs deux faces.</p> <p class="MsoNormal" style="text-align: justify; margin-left: 80">&nbsp;Dans le mme ordre dide, nous venons de prparer de nouvelles porphyrines di <b style="mso-bidi-font-weight:normal">7</b>, tetra <b style="mso-bidi-font-weight:normal">8a </b>et<b style="mso-bidi-font-weight: normal"> 8b</b> et hexa-amines <b style="mso-bidi-font-weight:normal">9</b>. Dans le cas o <b style="mso-bidi-font-weight:normal">8b</b> est condens  une anse binaphtyle chirale, nous avons obtenu un catalyseur dpoxydation asymtrique <b style="mso-bidi-font-weight:normal">exceptionnel 10</b> avec des turnovers suprieurs  <b style="mso-bidi-font-weight:normal">10 000/h</b> et avec des excs nantiomriques actuellement de <b style="mso-bidi-font-weight: normal">92%</b>! Il sagit avec <b style="mso-bidi-font-weight:normal">11, des deux</b> <b style="mso-bidi-font-weight:normal">premiers catalyseurs</b> porphyriniques aussi performants dcrits dans la littrature (Polyhedron, <b style="mso-bidi-font-weight:normal">2000</b> sous presse). En effet, nous avons obtenu aussi un catalyseur <b style="mso-bidi-font-weight:normal">11</b> drivant de latropoisomre <span style="font-family:Symbol">abab </span>de la ttrakis-(2-aminophnyl)porphyrine, qui donne des ee et des turnovers comparables  ceux obtenus avec le catalyseur <b style="mso-bidi-font-weight: normal">10</b> (<i style="mso-bidi-font-style:normal">J. Am. Chem. Soc.</i> <b style="mso-bidi-font-weight:normal">1999</b>, 121, 460) Ces deux rsultats exceptionnels sont dus au fait que le catalyseur se transforme immdiatement en un autre beaucoup plus efficace par oxydation du groupe mthoxy en dione <b style="mso-bidi-font-weight:normal">12</b>. Nous continuons activement cet axe de recherche car nos catalyseurs se trouvent tre les meilleurs dcrits dans la littrature pour lpoxydation des olfines terminales. Une deuxime communication (<i style="mso-bidi-font-style:normal">J. Am. Chem. Soc.</i> <b style="mso-bidi-font-weight:normal">1999</b>, 121, 2903) dcrit comment on peut utiliser loutil RMN du <sup>57</sup>Fe pour dterminer les dformations du plan des porphyrines.</p> <p class="MsoNormal" style="text-align: justify; margin-left: 80; margin-right: -9.25pt"><b style="mso-bidi-font-weight: normal">Perspectives</b></p> <p class="MsoNormal" style="text-align: justify; margin-left: 80">Nous prparons actuellement de nouveaux catalyseurs, en esprant augmenter non seulement les turnovers mais aussi lexcs nantiomrique en modifiant un peu lenvironnement du site actif dans le but datteindre 99% dee et des turnovers suprieurs  100 000/h. La synthse des porphyrines de type <b style="mso-bidi-font-weight:normal">6a</b>, <b style="mso-bidi-font-weight: normal">8</b>,<b style="mso-bidi-font-weight:normal"> 10 </b>et<b style="mso-bidi-font-weight:normal"> 11 </b>ouvre des perspectives non seulement d'un point de vue acadmique (synthse de modles d'hmoprotines) mais aussi d'un point de vue industriel (synthse de nouveaux catalyseurs chiraux en oxydation). Lhydroxylation asymtrique de liaisons C-H non actives constituera le nouveau dfi que nous comptons relever. Nous venons de prparer un nouveau modle de cytochrome c oxidase et en collaboration avec Bruno Andrioletti qui vient de rejoindre notre groupe de <b style="mso-bidi-font-weight: normal">nouveaux matriels macrocycliques et non porphyriniques</b> qui devraient dpasser les rsultats obtenus avec nos porphyrines chirales en oxydation asymtrique.</p> <p class="MsoNormal" style="text-align: justify; margin-left: 80"><span style="background-color: white; background-repeat: repeat; background-attachment: scroll; background-position: 0%"><a href="../../recher/activite.htm">Pour des informations complmentaires</a>...</span></p> <p class="MsoNormal" align="center"><a href="#0"><img border="0" src="../../../../images/lacot.2.gif" width="17" height="28"></a></p> <p class="MsoNormal" align="center" style="line-height: 18.0pt; margin-left: -1.0pt; margin-right: -9.25pt; margin-top: 0cm; margin-bottom: .0001pt"><img border="0" src="../../../../images/espace.jpg" width="80%" height="1%"></p> <p class="MsoNormal" align="center" style="line-height: 18.0pt; margin-left: -1.0pt; margin-right: -9.25pt; margin-top: 0cm; margin-bottom: .0001pt">&nbsp;</p> <p class="MsoNormal" align="left"><b><font size="4"><a name="3"></a>III) 7 PUBLICATIONS SIGNIFICATIVES</font></b></p> <p class="MsoNormal" style="text-align: justify; margin-left: 80; margin-top: 0; margin-bottom: 0"><span style="mso-bidi-font-weight: normal; mso-ansi-language: EN-GB" lang="EN-GB"><b style="mso-bidi-font-weight: normal; mso-ansi-language: EN-GB"><span style="mso-ansi-language: EN-GB; mso-bidi-font-weight: normal">1)<span style="mso-bidi-font-weight: normal; mso-ansi-language: EN-GB">&nbsp;&nbsp;&nbsp; </span></span></b><span style="mso-ansi-language: EN-GB; mso-bidi-font-weight: normal">Resolution and asymetric synthesis of ortho-substituted benzaldehydetricarbonylchromium complexes</span></span></p> <p class="MsoNormal" style="text-align: justify; margin-left: 80; margin-top: 0; margin-bottom: 0"><span lang="EN-GB" style="mso-ansi-language: EN-GB; mso-bidi-font-weight: normal">A. Alexakis, P. Mangeney, I. Marek, F. Rose-Munch, E. Rose, F. Robert</span></p> <p class="MsoNormal" style="text-align: justify; margin-left: 80; margin-top: 0; margin-bottom: 0"><span style="mso-bidi-font-weight: normal; mso-ansi-language: EN-GB" lang="EN-GB"><span style="mso-ansi-language: EN-GB; mso-bidi-font-weight: normal"><i><b>J. Am. Chem. Soc.,</b></i></span><b style="mso-bidi-font-weight: normal; mso-ansi-language: EN-GB"><span style="mso-ansi-language: EN-GB; mso-bidi-font-weight: normal"> 1992</span></b><span style="mso-ansi-language: EN-GB; mso-bidi-font-weight: normal">, <i style="mso-bidi-font-weight: normal; mso-ansi-language: EN-GB">114</i>, 8288-8290.</span></span></p> <p class="MsoNormal" style="text-align: justify; margin-left: 80; margin-top: 0; margin-bottom: 0"><span style="mso-ansi-language: EN-GB; mso-bidi-font-weight: normal" lang="EN-GB">&nbsp;</span></p> <p class="MsoNormal" style="text-align: justify; margin-left: 80; margin-top: 0; margin-bottom: 0"><span style="mso-bidi-font-weight: normal; mso-ansi-language: EN-GB" lang="EN-GB"><b style="mso-bidi-font-weight: normal; mso-ansi-language: EN-GB"><span style="mso-ansi-language: EN-GB; mso-bidi-font-weight: normal">2)</span></b><span style="mso-ansi-language: EN-GB; mso-bidi-font-weight: normal"> <span style="mso-bidi-font-weight: normal; mso-ansi-language: EN-GB">&nbsp;&nbsp; </span>Synthesis of Tricarbonyl( </span><span style="mso-bidi-font-weight: normal; mso-ansi-language: EN-GB">h</span><span style="mso-ansi-language: EN-GB; mso-bidi-font-weight: normal">5-cyclohexadienyl)chromium Complexes via Nucleophilic Addition of hydride on (</span><span style="mso-bidi-font-weight: normal; mso-ansi-language: EN-GB">h</span><span style="mso-ansi-language: EN-GB; mso-bidi-font-weight: normal">6-Arene)tricarbonylchromium Complexes</span></span></p> <p class="MsoNormal" style="text-align: justify; margin-left: 80; margin-top: 0; margin-bottom: 0"><span lang="EN-GB" style="mso-ansi-language: EN-GB; mso-bidi-font-weight: normal">J. P. Djukic, F. Rose-Munch, E. Rose, Y. Dromzee</span></p> <p class="MsoNormal" style="text-align: justify; margin-left: 80; margin-top: 0; margin-bottom: 0"><span style="mso-ansi-language: EN-GB; mso-bidi-font-weight: normal"><i><b>J. Am. Chem. Soc., </b></i> <b style="mso-bidi-font-weight: normal; mso-ansi-language: EN-GB">1993</b>, <i style="mso-bidi-font-weight: normal; mso-ansi-language: EN-GB">115</i>, 6434-6435.</span></p> <p class="MsoNormal" style="text-align: justify; margin-left: 80; margin-top: 0; margin-bottom: 0">&nbsp;</p> <p class="MsoNormal" style="text-align: justify; margin-left: 80; margin-top: 0; margin-bottom: 0"><span style="mso-bidi-font-weight: normal; mso-ansi-language: EN-GB" lang="EN-GB"><b style="mso-bidi-font-weight: normal; mso-ansi-language: EN-GB"><span style="mso-ansi-language: EN-GB; mso-bidi-font-weight: normal">3)</span></b><span style="mso-ansi-language: EN-GB; mso-bidi-font-weight: normal"><span style="mso-bidi-font-weight: normal; mso-ansi-language: EN-GB">&nbsp;&nbsp;&nbsp; </span>Synthesis of Biomimetic Heme Precursors: the &quot;Double Picket Fence&quot; Tetrakis 5, 10, 15, 20-(2', 6'-dinitro, 4'-tert-butylphenyl) porphyrin</span></span></p> <p class="MsoNormal" style="text-align: justify; margin-left: 80; margin-top: 0; margin-bottom: 0"><span style="mso-bidi-font-weight: normal; mso-ansi-language: EN-GB" lang="EN-GB">E. Rose, A. Kossanyi, M. Quelquejeu, N. Bernard, M. Soleilhavoup, F. Duwavran and A. Lecas</span></p> <p class="MsoNormal" style="text-align: justify; margin-left: 80; margin-top: 0; margin-bottom: 0"><span style="mso-ansi-language: EN-GB; mso-bidi-font-weight: normal"><b><i>J. Am. Chem. Soc.</i>, </b> <b style="mso-bidi-font-weight: normal; mso-ansi-language: EN-GB">1996</b>, <i style="mso-bidi-font-weight: normal; mso-ansi-language: EN-GB">118,</i> 1567-1568.</span></p> <p class="MsoNormal" style="text-align: justify; margin-left: 80; margin-top: 0; margin-bottom: 0">&nbsp;</p> <p class="MsoNormal" style="text-align: justify; margin-left: 80; margin-top: 0; margin-bottom: 0"><span lang="EN-GB" style="mso-ansi-language:EN-GB"><b style="mso-bidi-font-weight:normal">4)</b></span><span lang="EN-GB" style="mso-ansi-language:EN-GB"><span style="mso-tab-count:1">&nbsp;&nbsp;&nbsp; </span>Iron-57 Nuclear Shiedings as a quantitative Tool for Estimating Porphyrin Ruffling in hemoproteins and Model Compounds in Solution</span></p> <p class="MsoNormal" style="text-align: justify; text-indent: -.05pt; margin-left: 80; margin-top: 0; margin-bottom: 0"><span lang="EN-GB" style="mso-ansi-language:EN-GB">C.G. Kalodimos, I.P. Grothanassis, E. Rose, G.E. Hawkes, R. Pierattelli</span></p> <p class="MsoNormal" style="text-align: justify; text-indent: -21.25pt; margin-left: 80; margin-top: 0; margin-bottom: 0"><span style="mso-tab-count: 1; mso-ansi-language: EN-GB" lang="EN-GB"><i style="mso-bidi-font-style:normal"><b style="mso-bidi-font-weight:normal">&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;</b></i> </span><span style="mso-ansi-language: EN-GB; mso-bidi-font-weight: normal"><i><span style="mso-ansi-language: EN-GB; mso-bidi-font-weight: normal"><i style="mso-ansi-language: EN-GB; mso-bidi-font-weight: normal"> <b>J. Am. Chem. Soc.</b>,</i></span></i></span><span lang="EN-GB" style="mso-ansi-language: EN-GB"><i style="mso-bidi-font-style:normal"> </i> </span><b style="mso-bidi-font-weight:normal"><span lang="EN-GB" style="mso-ansi-language:EN-GB">1999</span></b><span lang="EN-GB" style="mso-ansi-language:EN-GB">, 121, 2903-2908.</span></p> <p class="MsoNormal" style="text-align: justify; margin-left: 80; margin-top: 0; margin-bottom: 0">&nbsp;</p> <p class="MsoNormal" style="text-align: justify; margin-left: 80; margin-top: 0; margin-bottom: 0"><span style="mso-bidi-font-weight: normal; mso-ansi-language: EN-GB" lang="EN-GB"><span style="mso-ansi-language: EN-GB; mso-bidi-font-weight: normal"><b style="mso-bidi-font-weight: normal; mso-ansi-language: EN-GB">5)</b><span style="mso-bidi-font-weight: normal; mso-ansi-language: EN-GB">&nbsp;&nbsp;&nbsp; </span>An efficient Catalyst for Asymmetric Epoxidation of terminal Olefins, </span></span></p> <p class="MsoNormal" style="text-align: justify; margin-left: 80; margin-top: 0; margin-bottom: 0"><span style="mso-ansi-language: EN-GB; mso-bidi-font-weight: normal" lang="EN-GB">J.P. Collman, A. Straumanis, Z. Wang, M. Quelquejeu, E.Rose </span></p> <p class="MsoNormal" style="text-align: justify; margin-left: 80; margin-top: 0; margin-bottom: 0"><b><i style="mso-bidi-font-weight: normal; mso-ansi-language: EN-GB"><span style="mso-ansi-language: EN-GB; mso-bidi-font-weight: normal" lang="EN-GB">J. Am</span></i><i style="mso-bidi-font-style:normal"><span lang="DE" style="mso-ansi-language: DE">. </span>Chem. Soc.,</i> </b> <b style="mso-bidi-font-weight:normal">1999</b>, 121, 460-461.</p> <p class="MsoNormal" style="text-align: justify; margin-left: 80; margin-top: 0; margin-bottom: 0">&nbsp;</p> <p class="MsoNormal" style="text-align: justify; margin-left: 80; margin-top: 0; margin-bottom: 0"><span style="mso-bidi-font-weight: normal; mso-ansi-language: EN-GB" lang="EN-GB"><b>6)</b></span>&nbsp;&nbsp;&nbsp; Synthesis of chiral porphyrins:models of natural hemoproteins and impressive catalysts for asymmetric epoxidation of olefins,</p> <p class="MsoNormal" style="text-align: justify; margin-left: 80; margin-top: 0; margin-bottom: 0">E.Rose, M.Quelquejeu, R.P.Pandian, A.Lecas-Nawrocka, A.Vilar, G.Ricart J-P.Collman,Z.Wang, A Strausmanis</p> <p class="MsoNormal" style="text-align: justify; margin-left: 80; margin-top: 0; margin-bottom: 0"><b><i>Polyhedron 2000</i></b>,19,581</p> <p class="MsoNormal" style="text-align: justify; margin-left: 80; margin-top: 0; margin-bottom: 0">&nbsp;</p> <p class="MsoNormal" style="text-align: justify; margin-left: 80; margin-top: 0; margin-bottom: 0"><b>7)&nbsp;&nbsp;</b>&nbsp;&nbsp; First Synthesis of a Chiral Strapped Binap-corrole</p> <p class="MsoNormal" style="text-align: justify; margin-left: 80; margin-top: 0; margin-bottom: 0">B. Andriolletti,E. Rose</p> <p class="MsoNormal" style="text-align: justify; margin-left: 80; margin-top: 0; margin-bottom: 0"><i>J.Chem. Soc.Perkin 1</i>,<b>2002</b> 715</p> <p class="MsoNormal" align="center"><a href="#0"><img border="0" src="../../../../images/lacot.2.gif" width="17" height="28"></a></p> <p class="MsoNormal" align="center" style="line-height: 18.0pt; margin-left: -1.0pt; margin-right: -9.25pt; margin-top: 0cm; margin-bottom: .0001pt"><img border="0" src="../../../../images/espace.jpg" width="80%" height="1%"></p> <p class="MsoBodyTextIndent" style="line-height: 150%; margin-left: 0" align="left"><b><font size="4"><a name="4"></a>IV)   COLLABORATIONS NATIONALES</font></b></p> <p class="MsoBodyTextIndent" style="line-height: 150%; margin-left: 80"><span style="font-size: 12.0pt;mso-bidi-font-size:10.0pt"><img border="0" src="../../../../images/red.gif" width="14" height="14">  Pr. David Aitken (Universit Blaise Pascal, Clermont-Ferrand-France)</span></p> <p class="MsoBodyTextIndent" style="line-height: 150%; margin-left: 80"><span style="font-size: 12.0pt;mso-bidi-font-size:10.0pt"><img border="0" src="../../../../images/red.gif" width="14" height="14">  Pr. Alex Alexakis (Universit de Genve, Suisse)</span></p> <p class="MsoBodyTextIndent" style="line-height: 150%; margin-left: 80"><span style="font-size: 12.0pt;mso-bidi-font-size:10.0pt"><img border="0" src="../../../../images/red.gif" width="14" height="14"> Dr. B. Boitrel (Universit de Bourgogne, Dijon-France)</span></p> <p class="MsoBodyTextIndent" style="line-height: 150%; margin-left: 80"><span style="font-size: 12.0pt;mso-bidi-font-size:10.0pt"><img border="0" src="../../../../images/red.gif" width="14" height="14"> Dr. Doris Lexa (Universit de la Mditerrane, Marseille-France)</span></p> <p class="MsoBodyTextIndent" style="line-height: 150%; margin-left: 80"><span style="font-size: 12.0pt;mso-bidi-font-size:10.0pt"><img border="0" src="../../../../images/red.gif" width="14" height="14">  Pr. Claude Mose (Universit de Bourgogne, Dijon-France)</span></p> <p class="MsoBodyTextIndent" style="line-height: 150%; margin-left: 80"><span style="font-size: 12.0pt;mso-bidi-font-size:10.0pt"><img border="0" src="../../../../images/red.gif" width="14" height="14"> Pr. JL Namy (Universit Paris-sud XI, Orsay-France)</span></p> <p class="MsoBodyTextIndent" style="line-height: 150%; margin-left: 80"><span style="font-size: 12.0pt;mso-bidi-font-size:10.0pt"><img border="0" src="../../../../images/red.gif" width="14" height="14"> Yves Troin (Universit Blaise Pascal, Clermont-Ferrand-France)</span></p> <p class="MsoBodyTextIndent" style="line-height: 150%; margin-left: 80"><span style="font-size: 12.0pt;mso-bidi-font-size:10.0pt"><img border="0" src="../../../../images/red.gif" width="14" height="14">  Dr. Jacqueline Vaisserman (Universit Pierre et Marie Curie, Paris-France)</span></p> <p class="MsoBodyTextIndent" align="center"><a href="#0"><img border="0" src="../../../../images/lacot.2.gif" width="17" height="28"></a></p> <p class="MsoBodyTextIndent" align="center"><img border="0" src="../../../../images/espace.jpg" width="80%" height="1%"></p> <p class="MsoNormal" style="margin-left: 0"><b style="mso-bidi-font-weight:normal"><span style="font-size:14.0pt;mso-bidi-font-size:10.0pt"><a name="5"></a>V)   COLLABORATIONS INTERNATIONALES</span></b></p> <p class="MsoNormal" style="margin-left: 80"><span style="font-size: 12.0pt;mso-bidi-font-size:10.0pt"><img border="0" src="../../../../images/red.gif" width="14" height="14"> </span>Prof. J.P. Collman (Stanford University, CA, USA)</p> <p class="MsoNormal" style="margin-left: 80"><span style="font-size: 12.0pt;mso-bidi-font-size:10.0pt"><img border="0" src="../../../../images/red.gif" width="14" height="14"> </span>Prof. H. Garcia (Lisbonne, Portugal)</p> <p class="MsoNormal" style="margin-left: 80"><span style="font-size: 12.0pt;mso-bidi-font-size:10.0pt"><img border="0" src="../../../../images/red.gif" width="14" height="14"> </span><span lang="EN-GB" style="mso-ansi-language:EN-GB">Prof. I.P. Gerothanassis (Greece)</span></p> <p class="MsoNormal" style="margin-left: 80"><span style="font-size: 12.0pt;mso-bidi-font-size:10.0pt"><img border="0" src="../../../../images/red.gif" width="14" height="14"> </span>Prof. J. Heck (Hamburg, Deutchland),</p> <p class="MsoNormal" style="margin-left: 80"><span style="font-size: 12.0pt;mso-bidi-font-size:10.0pt"><img border="0" src="../../../../images/red.gif" width="14" height="14"> </span>Doc. 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