BARRELENEIRIDIUM(I) COMPLEXES. CRYSTAL STRUCTURES OF 6-C6H4Me2)>ClO4 and 5-PhNPh2)>BF4*CH2Cl2 (TFB = tetrafluorobenzobarrelene)

Article abstract of DOI:10.1016/0022-328X(84)80511-2

A new series of cationic areneiridium(I) complexes of formula ⁺ or ⁺ (R = Ph or H) have been synthesized from neutral iridium complexes of the type x (barrelene = Me3TFB, Y = Cl or OMe (x = 2, Y = acac (x = 1); barrelene = TFB, Y = OMe (x = 2), Y = acac (x = 1)).The crystal structures of ClO4 and BF4*CH2Cl2 have been determined by X-ray diffraction.They crystallize in the space groups Pbca and Pna2₁ respectively with lattice constants of 17.6947(11), 15.8072(10), 16.0019(11) Angstroem and 9.8059(2), 20.8097(9), 14.3367(4) Angstroem.Final R factors were 0.063 and 0.042 for the observed data.Both complexes show a staggered arrangement between the arene and the TFB moieties and deviation from planarity of the coordinated arene ligands.In the second complex the Ir-C and N-C distances, the C-N-C angle, the type of arene puckering, and the spectroscopic data indicate a distortion of the coordinated arene towrads a η⁵-coordinated iminocyclohexadienyl form.