Abstract
The X-ray diffraction analysis of (η 4-chd) 2Ir-2-furyl (chd = cyclohexa-1,3-diene) proves its square-pyramidal geometry and supine-supine orientation of the diene ligands. A model computation for the corresponding 2-N-methylpyrrolyl complex shows the N-methyl group to be responsible for hindered rotation of the σ-bonded ligand. Protonation of the heteroaryl complexes (η 4-chd) 2IrR (R = 2-furyl, 2-thienyl, 2-N-methylpyrrolyl) by CF 3CO 2H yields the novel compounds [(η 4-chd) 2Ir( CCHCHCH 2X )] +CF 3CO 2 − (X = O, S, NCH 3) which can best be described as ylides. In the furyl case, the reaction is shown to be reversible. With excess PMe 3, the neutral species undergo ligand substitution to form (η 4-chd)(PMe 3) 2Ir(C 4H 3X) (X = O, S), while attempts to isolate the corresponding derivative with X = NCH 3 failed.
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