Lithium complexes phthalocyanines

Dilithium phthalocyanine was originally prepared from lithium amyl-oxide and phthalonitrile in boiling amyl alcohol 11), but may also be prepared from lithium hydride 53) or lithium metal 214) and phthalonitrile. It is readily purified by recrystallization from acetone. A monolithium derivative, presumably lithium hydrogen phthalocyanine, is formed when a deficiency of lithium or lithium salt is used in these reactions. It is a black insoluble compound of unknown structure 11). The high solubility of the dilithium complex makes it a very useful intermediate in double decomposition reactions. Many comparatively unstable metal phthalocyanines can be formed by the reaction of dilithium phthalocyanine and the appropriate metal salt in a solvent such as acetone, dimethylformamide, or quinoline 11, 119, 120). 

Although direct reaction of lanthanide mono-porphyrins with free phthalo-cyanine or its lithium derivatives is generally more efficient than the template synthesis, and gives rise to mixed-ligand complexes, the template strategy can also be applied for synthesis of phthalocyanine-porphyrin complexes, as in the case of unsymmetric bisphthalocyanine complexes (Scheme 8.2, B(b)) [106, 136, 145, 146]. Thus, metallation of free porphyrins with lanthanide salts in TCB or n-octanol leads to single-decker complexes, which then react with phthalonitriles under the action of DBU in alcoholic media to give the desired compounds. 

For the insertion of noble metal ions into phthalocyanine H2(Pc), the latter is favorably activated by transformation into its lithium derivative. Thus, reaction of Li2(Pc) with [Rh(COD)Cl]2 in a large excess of a donor solvent L yielded the Rh(II) complexes, Rh(Pc) L2 (L = Py, BuNH2, Bipy, Pyz) [119]. The formation of these Rh(II) species is very remarkable because Rh insertions normally yield either Rh(I) or Rh(III) derivatives. Recently, tris(ethylenediamine)-rhodium(III) iodide [Rh(en)3]I3 and phthalodinitrile have been used to prepare H [RhI2(Pc)] 2phthalodinitrile. This material was then transformed into [Rh(OH)2(Pc)] by treatment with first H2SQ4 and then KOH. Treatment of... 

The phthalocyanine radical complex of lithium (PcLi ) is a member of the class of intrinsic molecular semiconductors [27]. Its preparation is carried out by electrosynthesis at 70°C under... 

Reports of initial work indicated that uranyl phthalocyanine complexes could be obtained from the reaction of bis(dimethylformamide)uranyl acetate with lithium phthalocyanine [ 113], or the reaction of uranyl acetate with phthalocyanine [114,115j. However, in 1964, Bloor et al. [116] reported that the reaction of uranyl... 

Phthalocyanine complexes exhibit magnetic moments corresponding to low-spin, electron-paired species (57). One exception is lithium phthalocyanine manganate(O), a spin-free case which may occur for metals in their lowest oxidation state (57). On the basis of the low spin observed for phthalocyaninechromium(II) and phthalocyaninechloroiron(III), a metal-metal interaction which extends throughout the lattice has been postulated (55),... 

Reports of examples of arylphosphonates include those of water-soluble phosphinic-polyphosphonic acids, e.g. 132, and the phosphonate 133 which when coupled to alcohols, to give e.g. 134, act as linkers to proteins in experiments intended to generate antibodies to catalyse cationic cyclisation reactions.Novel water-soluble phosphonate-substituted phthalocyanines have been prepared.The phosphonate esters 135 are insoluble in water but can be hydrolysed by hydrochloric acid to give the water-soluble phosphonic acids 136. Aromatic phosphonate-phosphines 137, and their air-stable complexes, have been obtained from the reaction of 4-halogeno-substituted phenylphosphonates with lithium diphenylphosphide. ... 

Palladium chlorophthalocyanine is formed when phthalonitrile is heated with palladous chloride. Like other nuclear halogen-substituted phthalocyanines, it will not sublime (11, 278). The unsubstituted derivative may be prepared by the dehydrogenation of tetracyclohexenotetrazaporphin with palladium black (113), or by the action of palladous chloride on lithium phthalocyanine in absolute alcohol (11). It is also possible to prepare the complex by dissolving palladium black in boiling phthalonitrile, a really remarkable reaction. 

Lithium alkoxides play an important role in the oligomeric cyclization of dinitriles in the synthesis of phthalocyanines. The combination of potassium alkoxide-crown ether complex in a hydrocarbon solvent gives a very powerful catalyst for production of vinyl ethers from alcohols and acetylene (Eq. 7.9). ... 

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