The Stereospecific Ligand Exchange at a Pseudo‐Benzylic T‐4 Iridium Centre in Planar‐Chiral Cycloiridium (η6‐Arene)tricarbonylchromium Complexes
Identifieur interne : 001158 ( Main/Exploration ); précédent : 001157; suivant : 001159The Stereospecific Ligand Exchange at a Pseudo‐Benzylic T‐4 Iridium Centre in Planar‐Chiral Cycloiridium (η6‐Arene)tricarbonylchromium Complexes
Auteurs : Jean-Pierre Djukic [France] ; Cédric Boulho ; Dusan Sredojevic [Serbie] ; Carla Scheeren ; Snezana Zaric [Serbie] ; Louis Ricard [France] ; Michel PfefferSource :
- Chemistry – A European Journal [ 0947-6539 ] ; 2009-10-19.
English descriptors
Abstract
The stereospecificity of ligand exchange at the IrIII centre of a cycloiridium arenetricarbonylchromium complex has been established experimentally by various analytical methods as well as by X‐ray diffraction structural analysis and computational investigations. Two new cases of phenyl and methyl iridium(III) complexes have been prepared by reaction of (${S{{{\ast}\hfill \atop {\rm p}\hfill}}}$,${R{{{\ast}\hfill \atop {\rm Ir}\hfill}}}$)‐chlorido{2‐[(tricarbonyl)(η6‐phenylene‐κC1′)chromium(0)]pyridine‐κN}(pentamethylcyclopentadienyl)iridium(III) with PhMgBr and MeMgBr. The determining influence of electrostatic repulsion has been established by means of density functional theory at the Becke–Perdew/TZP(ZORA) level by using, among other means, energy partitioning analysis. It is also shown that the Cr(CO)3 fragment is likely to ease the ionic cleavage of the IrCl bond in chlorido cycloiridium tricarbonylchromium complexes in a way similar to that already established for the solvolysis of benzyl halide complexes, that is, through a direct interaction of the Cr0 centre with the cationic IrIII centre.
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DOI: 10.1002/chem.200901344
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Two new cases of phenyl and methyl iridium(III) complexes have been prepared by reaction of (${S{{{\ast}\hfill \atop {\rm p}\hfill}}}$,${R{{{\ast}\hfill \atop {\rm Ir}\hfill}}}$)‐chlorido{2‐[(tricarbonyl)(η6‐phenylene‐κC1′)chromium(0)]pyridine‐κN}(pentamethylcyclopentadienyl)iridium(III) with PhMgBr and MeMgBr. The determining influence of electrostatic repulsion has been established by means of density functional theory at the Becke–Perdew/TZP(ZORA) level by using, among other means, energy partitioning analysis. It is also shown that the Cr(CO)3 fragment is likely to ease the ionic cleavage of the IrCl bond in chlorido cycloiridium tricarbonylchromium complexes in a way similar to that already established for the solvolysis of benzyl halide complexes, that is, through a direct interaction of the Cr0 centre with the cationic IrIII centre.</div></front></TEI><affiliations><list><country><li>France</li><li>Serbie</li></country></list><tree><noCountry><name sortKey="Boulho, Cedric" sort="Boulho, Cedric" uniqKey="Boulho C" first="Cédric" last="Boulho">Cédric Boulho</name><name sortKey="Pfeffer, Michel" sort="Pfeffer, Michel" uniqKey="Pfeffer M" first="Michel" last="Pfeffer">Michel Pfeffer</name><name sortKey="Scheeren, Carla" sort="Scheeren, Carla" uniqKey="Scheeren C" first="Carla" last="Scheeren">Carla Scheeren</name></noCountry><country name="France"><noRegion><name sortKey="Djukic, Jean Ierre" sort="Djukic, Jean Ierre" uniqKey="Djukic J" first="Jean-Pierre" last="Djukic">Jean-Pierre Djukic</name></noRegion><name sortKey="Ricard, Louis" sort="Ricard, Louis" uniqKey="Ricard L" first="Louis" last="Ricard">Louis Ricard</name></country><country name="Serbie"><noRegion><name sortKey="Sredojevic, Dusan" sort="Sredojevic, Dusan" uniqKey="Sredojevic D" first="Dusan" last="Sredojevic">Dusan Sredojevic</name></noRegion><name sortKey="Zaric, Snezana" sort="Zaric, Snezana" uniqKey="Zaric S" first="Snezana" last="Zaric">Snezana Zaric</name></country></tree></affiliations></record>Pour manipuler ce document sous Unix (Dilib)
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