Phthalocyanine nickel derivative

In an interesting study, phthalocyanine complexes containing four anthraquinone nuclei (5.34) were synthesised and evaluated as potential vat dyes and pigments [18]. Anthraquinone-1,2-dicarbonitrile or the corresponding dicarboxylic anhydride was reacted with a transition-metal salt, namely vanadium, chromium, iron, cobalt, nickel, copper, tin, platinum or lead (Scheme 5.6). Substituted analogues were also prepared from amino, chloro or nitro derivatives of anthraquinone-l,2-dicarboxylic anhydride. 

We can now make sensible guesses as to the order of rate constant for water replacement from coordination complexes of the metals tabulated. (With the formation of fused rings these relationships may no longer apply. Consider, for example, the slow reactions of metal ions with porphyrine derivatives (20) or with tetrasulfonated phthalocyanine, where the rate determining step in the incorporation of metal ion is the dissociation of the pyrrole N-H bond (164).) The reason for many earlier (mostly qualitative) observations on the behavior of complex ions can now be understood. The relative reaction rates of cations with the anion of thenoyltrifluoroacetone (113) and metal-aqua water exchange data from NMR studies (69) are much as expected. The rapid exchange of CN " with Hg(CN)4 2 or Zn(CN)4-2 or the very slow Hg(CN)+, Hg+2 isotopic exchange can be understood, when the dissociative rate constants are estimated. Reactions of the type M+a + L b = ML+(a "b) can be justifiably assumed rapid in the proposed mechanisms for the redox reactions of iron(III) with iodide (47) or thiosulfate (93) ions or when copper(II) reacts with cyanide ions (9). Finally relations between kinetic and thermodynamic parameters are shown by a variety of complex ions since the dissociation rate constant dominates the thermodynamic stability constant of the complex (127). A recently observed linear relation between the rate constant for dissociation of nickel complexes with a variety of pyridine bases and the acidity constant of the base arises from the constancy of the formation rate constant for these complexes (87). 

Fuel cells - [FUEL CELLS] (Vol 11) - [ELECTROCHEMICALPROCESSING - INTRODUCTION] (Vol9) -ceramics m [CERAMICS AS ELECTRICAL MATERIALS] (Vol 5) -as fuel resources [FUEL RESOURCES] (Vol 12) -hydrazine in [HYDRAZINE AND ITS DERIVATIVES] (Vol 13) -lanthanides for [LANTHANIDES] (Vol 14) -lithium carbonate m [LITHIUM AND LITHIUM COMPOUNDS] (Vol 15) -nickel and nickel alloys m [NICKEL AND NICKEL ALLOYS] (Vol 17) -phthalocyamnes m [PHTHALOCYANINE COMPOUNDS] (Vol 18) -platinum-group metal catalysts for [PLATINUM-GROUP METALS] (Vol 19) -for power generation [POWER GENERATION] (Vol 20) -use of hydrides m [HYDRIDES] (Vol 13) -use of nickel compounds [NICKEL COMPOUNDS] (Vol 17)... 

Zhang and Rusling [66] employed a stable, conductive, bicontinuous microemulsion of surfactant/oil/water as a medium for catalytic dechlorination of PCBs at about 1 mA cm-2 on Pb cathodes. The major products were biphenyl and its reduced alkylbenzene derivatives, which are much less toxic than PCBs. Zinc phthalocyanine provided better catalysis than nickel phthalocyanine tetrasulfonate. The current efficiency was about 20% for 4,4 -DCB and about 40% for the most heavily chlorinated PCB mixture. A nearly complete dechlorination of 100 mg of Aroclor 1260 with 60% Cl was achieved in 18 hr. Electrochemical dehalogenation was thus shown to be feasible in water-based surfactant media, providing a lower-cost, safer alternative to toxic organic solvents. 

Fig. 17 Phthalocyanine derivatives forming fibers in solution, (a) Homochiral nickel(II) phthalo-cyanine 22. (b) Tetra(perylenediimide)phthalocyanine 23...

The 31P NMR spectra of nickel and zinc complexes of tetrakis(ethyl-phenylphosphinate)-substituted phthalocyanines showed the presence of several constitutional isomers.398 The formation of trimetallic (Ni2Pt) complexes by the reaction of nickel me.vo-tetratolylporphyrin derivatives with PtCl2-con-taining species has been shown by H and 13C NMR spectroscopy to be diastereoselective.399 The 111 NMR spectrum of nickel(II) umecyanin (a stellacyanin with an axial Glu ligand, demonstrates the unidentate coordination of Glu via the side-chain amode oxygen atom.400... 

Nickel phthalocyanine is conveniently prepared by heating etched nickel foil in o-cyanobenzamide at 270°C (10). An alternative preparation involves phthahc anhydride, urea, nickel chloride hexahydrate, and ammonium molybdate in trichlorobenzene at 200°C (81). It is stable to concentrated sulfuric acid, sublimes readily, and shows no tendency to form six-coordinate derivatives (10, 213, 325). 

Certain metal derivatives, particularly the ferrous and chloroferric complexes, catalyze the decomposition of hydrogen peroxide. They are themselves destroyed in the process (58, 127, 871). Paquot and his coworkers have extensively investigated the catalytic properties of the phthalocyanines (71, 270-277). Nickel phthalocyanine is a useful catalyst for the autoxidation of a-carbon atoms of ethylenic molecules. Thus nickel phthalocyanine (0.4%) catalyzes the aerial oxidation of cyclo-... 

Substantial efforts have been made to produce electrical conducting conjugated rigid-rod polymers, including PBZT, PBZO, and their derivatives. PBZT fibers spim from nickel phthalocyanine solutions and followed by chemical... 

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