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Die oxidative Addition von I2 an Tetrakis‐ [dithioacetatol]‐dinickel (I) führt zu dem linearen Kettenpolymeren (II), in dem der formale Oxidationszustand der Ni‐Atome + 2.5 beträgt.

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A new synthesis of dichloro(phthalocyaninato)titanium(IV), [C32H16N8Cl2Ti] (PcTiCl2), has been performed from phthalodinitrile and titanium tetrachloride in -chloronaphthalene. Substitution reactions of the chloride ions in PcTiCl2 lead to the formation of complexes of formula PcTiX, where X = catecholate (C6H4021 2~), oxalate (C2042™), and peroxide (022~) groups. These compounds have also been obtained by using PcTiO as starting material. Interconversion of all these species has been examined and their structure discussed on the basis of their chemical and physical behavior. Single crystals of the title compound were obtained under controlled conditions, and its X-ray crystal structure has been solved. Crystals of PcTiCl2 are triclinic (Pi) with a = 8.744 (9) A, b = 12.244 (4) A, c = 12.835 (4) A, a = 79.73 (3)°, ß = 95.32 (6)°, = 103.27 (6)°, and Z = 2. The two chlorine atoms are bound to the titanium atom in a cis position (Cl-Ti-Cl angle 82.4°) with respect to the plane of the phthalocyanine molecule, with the metal considerably displaced out of the plane of the N4 chromophore (CtN<-Ti distance 0.84 A) toward the two chlorine atoms (average Ti-Cl and Ti-N bond distances 2.087 and 2.317 A, respectively). The Cl-Ti-Cl moiety appears to choose an intermediate position between the eclipsed and the staggered conformation relative to the Ti-N4 bond system. The structural conformation of PcTiCl2 is discussed in relation to the structure of similar species already known from the literature.

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