Preparation and Molecular Structure

The phthalocyanines often exist in two or more polymorphic modifications, which may be distinguished by infrared and X-ray diffraction techniques (see Section D). Although phthalocyanines in which the central metal ion has an oxidation state of 2 are the most common, complexes are 

Phthalocyanine metal complexes may be prepared by various methods, the more general methods 10, 11, 34, 40, 86, 112) being illustrated in the following equations  

Reactions (III) and (IV) may also be carried out with metal salts or metal oxides  

Metal-free phthalocyanine may be prepared by a number of routes of which examples are given below. 

Equations (II) to (IX) illustrate basic methods of preparation, but many variations are used, particularly in industry, to obtain an economic yield. Phthalic acid, phthalamide, phthalimide, and phthalic anhydride, together with urea, are often used instead of phthalonitrile, and catalysts such as ammonium molybdate or zirconium tetrachloride may be employed (249, 251, 269). The reaction between phthalonitrile and metals (finely divided or acid-etched) is usually very vigorous at 250°-300°C, sufficient heat being generated to maintain the reaction temperature. This is an illustration of the ease with which the phthalocyanine skeleton is formed. Even more surprising are the observations that palladium black (118) and gold (189) will dissolve in molten phthalonitrile. Reaction (III) between phthalonitrile and a finely divided metal, metal hydride, oxide, or chloride is perhaps the most generally employed. For the unstable phthalocyanine complexes such as that of silver (11), the double decomposition reaction 

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Reactions with Halogens and Sulfur Oxychlorides Preparation and Molecular Structure of S4N5CI and SjNg... 

This chapter describes the preparation and molecular structure of a compound, 1, in which hydrazine itself is coordinated to two molybdenum atoms. 

Figure 4.2 Structure of [La(l)4Cp3S03] + [3]. (Reproduced with permission from H. Paul, P.H. Smith and K.N. Raymond, A lanthanide-amine template synthesis. Preparation and molecular structures of Ln(L)(CH3CN)(Cp3S03)3 [L= l,9-bis(2-aminoethyl)-l,4,6,9,12,14-hexaazacyclohexadecane Ln = La, Yb] and La(en)4(CH3CN)(Cp3S03)3, Inorganic Chemistry, 24, 3469, 1985. 1985 American Chemical Society.)...

Scheme 2.8.8 Preparation and molecular structure of complex 19. Phenyl groups at the phosphorus atoms have been omitted for clarity...

The interest in organic metals is largely due to opportunities for their practical application instead of common materials in electronics, optics, batteries, and other areas. The typical representative of the polyconjugated organic polymers is polyacetylene (PA). Because of the simplicity of its preparation and molecular structure, PA may be considered a prototype for the whole class of organic metals. It became a basic model for the verification of modem concepts of conductivity [2-9]. 

The preparation and molecular structure of [Fe(C(CHPh)CsCPh)-(dmpe)2][BPh4].Me2C0, where the l,4-diphenyl-l-yn-3-en-3-yl ligand is acting as an ti ,(1-) ligand have been described . 

Figure 15.6 Preparation and molecular structure of N-(3-triethoxysilylpropane)-i-pyrene-methaneimine...

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