TRANS-BIS(TRIPHENYLPHOSPHINE)PHTHALOCYANI NATO(2-)RHENIUM(II) - SYNTHESIS, PROPERTIES, AND CRYSTAL-STRUCTURE

Dirheniumheptoxide reacts with phthalodinitrile in boiling 1-chloronap hthalene and subsequent reprecipitation of the green raw product from cone. sulfuric acid to yield an oxo-phthalocyaninate of rhenium, which is reduced by molten triphenylphosphine forming dark green trans-bis riphenylphosphine)phthalocyaninato(2-)rhenium(II), (trans)[Re(PPh3)(2) pc(2-)]. The latter crystallizes triclinic in the space group P (1) ov er bar with the cell parameters as follows: a = 11.512(2) Angstrom, b = 12.795(2) Angstrom, c = 12.858(2) Angstrom, alpha = 64.42(2)degrees, beta = 79.45(2)degrees, gamma = 72.74(1)degrees; V = 1628.1(5); Z = 1 . Re is in the centre of the (N-p)(4) plane (N-p: N1, N3) and coordina tes two triphenylphosphine ligands axially in trans position. The aver age Re-N-p and Re-P distances are 2.007(1) and 2.516(3) Angstrom, resp ectively. Despite the many extra bands the typical B, Q and N regions of the pc(2-) ligand are observed at ca. 16500, 28900/32900 and 35300 cm(-1). A weak band group at ca. 8900 cm(-1) is attributed to a trip-m ultiplet transition, another one at ca. 14500 cm(-1) to a P --> Re cha rge transfer. The vibrational spectra are dominated by internal vibrat ions of the pc(2-) ligand. The very weak intensity of the IR bands at 905 and 1327 cm(-1) are diagnostic of the presence of Re-II.