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 b is(phthalocyaninato)tin(IV), Pc2Sn, with 12 and HNO3 lead to the forma tion 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 speci es [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 comp lex crystallizes in the tetragonal system. Unit cell data: formula C64 H32I2N16Ti, M = 1326.8, a = b = 13.841(3) angstrom, c = 6.370(3) angst rom, 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 consist ing of I3- units. In the 'sandwiched' unit (a) the two interligand C-C sigma bonds observed in Pc2Ti are no longer present, the new correspo nding 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 titani um 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, an d (d) the distance between the two N4 planes is 2.42 angstrom, which i mplies 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 it s Ti analogue. The nitrate and hexafluorophosphate derivatives are obt ained as amorphous materials. Dc electrical conductivity of all the do ped materials was measured on powdered compressed samples by Van der P auw's method, and the values obtained are discussed in the light of th e available crystallographic information, data from IR, resonance Rama n, UV-visible, and EPR spectra, and thermogravimetric analysis. A poss ible explanation is provided for the higher electrical conductivity ob served for the Sn complexes compared to that of the Ti complexes.