INTERLIGAND C-C SIGMA-BOND BREAKING AND REPAIR IN A STAPLED BIS(PHTHALOCYANINATO)TITANIUM COMPLEX - SYNTHESIS, CHARACTERIZATION, AND ELECTRICAL-CONDUCTIVITY PROPERTIES OF OXIDATION-PRODUCTS OF BIS(PHTHALOCYANINATO)TITANIUM(IV) AND BIS(PHTHALOCYANINATO)TIN(IV) AND X-RAY CRYSTAL-STRUCTURE OF [PC2TI](I3)0.66

Oxidation reactions of bis(phthalocyaninato)titanium(IV), Pc2Ti, and bis(phthalocyaninato)tin(IV), Pc2Sn, with 12 and HNO3 lead to the formation of the species [Pc2M](I3)0.66 and [PC2M]NO3, respectively [M = Ti(IV), Sn(IV)]. Exchange of the NO3- group with PF6- leads to the species [PC2M]PF6. Reduction of these oxidized saltlike species with NaBH4 results in the formation of the respective precursors PC2Ti and PC2Sn. The structure of the complex [PC2Ti](I3)0.66 has been elucidated by a low-temperature (-160-degrees-C) single-crystal X-ray study. The complex crystallizes in the tetragonal system. Unit cell data: formula C64H32I2N16Ti, M = 1326.8, a = b = 13.841(3) angstrom, c = 6.370(3) angstrom, V = 1220.3(7) angstrom3, Z = 1, space group P4/mcc. The structure of [PC2Ti](I3)0.66 shows columnar stacks of nonintegrally positively charged [PC2Ti]0.66+ units and parallel chains of iodine atoms consisting of I3- units. In the 'sandwiched' unit (a) the two interligand C-C sigma bonds observed in Pc2Ti are no longer present, the new corresponding C-C distance being 2.839 A, (b) the two Pc groups are staggered at an angle of 41.1-degrees, (c) as in the precursor PC2Ti, the titanium atom is surrounded by the eight inner nitrogen atoms in the form of a square antiprism, with Ti-N bond distances of 2.246(7) angstrom, and (d) the distance between the two N4 planes is 2.42 angstrom, which implies a distance of 1.21 angstrom of Ti to the center of its adjacent N4 plane. Solid crystalline [PC2Sn] (13)0.66 is isostructural with its Ti analogue. The nitrate and hexafluorophosphate derivatives are obtained as amorphous materials. Dc electrical conductivity of all the doped materials was measured on powdered compressed samples by Van der Pauw's method, and the values obtained are discussed in the light of the available crystallographic information, data from IR, resonance Raman, UV-visible, and EPR spectra, and thermogravimetric analysis. A possible explanation is provided for the higher electrical conductivity observed for the Sn complexes compared to that of the Ti complexes.