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The Stereospecific Ligand Exchange at a Pseudo‐Benzylic T ‐4 Iridium Centre in Planar‐Chiral Cycloiridium (η 6 ‐Arene)tricarbonylchromium Complexes
Author(s) -
Djukic JeanPierre,
Boulho Cédric,
Sredojevic Dusan,
Scheeren Carla,
Zaric Snezana,
Ricard Louis,
Pfeffer Michel
Publication year - 2009
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.200901344
Subject(s) - iridium , chemistry , pyridine , crystallography , ionic bonding , ligand (biochemistry) , stereospecificity , halide , chromium , cationic polymerization , ternary operation , medicinal chemistry , polymer chemistry , inorganic chemistry , ion , catalysis , organic chemistry , computer science , programming language , biochemistry , receptor
The stereospecificity of ligand exchange at the Ir III 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)(η 6 ‐phenylene‐κ C 1′ )chromium(0)]pyridine‐κ N }(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 Cr 0 centre with the cationic Ir III centre.