title: Synthesis of planar chiral iridacycles by cationic metal π-coordination: facial selectivity, and conformational and stereochemical consequences.
abstract: Facial selectivity during the π-coordination of pseudo-tetrahedral iridacycles by neutral (Cr(CO)(3)), monocationic (Cp*Ru(+)), and biscationic (Cp*Ir(2+)) metal centers was directly influenced by the coulombic imbalance in the coordination sphere of the chelated Ir center. We also showed by using theoretical calculations that the feasibility of the related metallacycles that displayed metallocenic planar chirality was dependent to the presence of an electron-donating group, such as NMe(2), which contributed to the overall stability of the complexes. When the π-bonded moiety was the strongly electron-withdrawing Cp*Ir(2+) group, the electron donation from NMe(2) resulted in major conformational changes, with a barrier to rotation of about 17 kcal  mol(-1) for this group that became spectroscopically diastereotopic (high-field (1)H NMR spectroscopy). This peculiar property is proposed as a means to introduce a new type of constitutional chirality at the nitrogen center: planar chirality at tertiary aromatic amines.
authors.affiliation: Institut de Chimie, CNRS, Université de Strasbourg, 4 rue Blaise Pascal, 67008 Strasbourg Cedex, France. djukic@unistra.fr
authors.forename: Jean-Pierre
authors.initials: JP
authors.lastname: Djukic
authors.forename: Wissam
authors.initials: W
authors.lastname: Iali
authors.forename: Michel
authors.initials: M
authors.lastname: Pfeffer
authors.forename: Xavier-Frédéric
authors.initials: XF
authors.lastname: Le Goff