Beryllium phthalocyanine

Beryllium phthalocyanine (PcBe) can be obtained by heating a mixture of phthalonitrile and beryllium metal, which has to be activated beforehand by etching with dilute acid.58... 

Beryllium metal, previously etched with acid, reacts with phthalonitrile to yield beryllium phthalocyanine, the only square planar derivative of beryllium known (10). Both anhydrous beryllium and magnesium phthalocyanines react readily with moisture to form very stable dihydrates. Dehydration may be effected only by sublimation in vacuo. Sidorov has studied the interaction of sublimed layers of beryllium and magnesium phthalocyanines with water, by infrared spectroscopy (825). Some of the absorption bands arising from the phthalocyanine unit shift when water vapor is introduced. This behavior was not noted with other phthalocyanines (see Section VI,A). 

Where the valency of a metal is not indicated, the normal valency of the metal is assumed. Beryllium probably is placed in the 0=N group because of the stability of its phthalocyanine chelate. Most often Be forms very stable bonds with oxygen as the donor element. Vanadium, nickel, and copper from the N > O group and iron from the ON group are the elements most frequently found in petroleum, chelated with porphyrin ligands. The porphyrin chelate contains four nitrogens as donor elements. 

In the metal derivatives of phthalocyanine the metal atoms are coordinated by four atoms of nitrogen at the corners of a square, and this arrangement suggests that these atoms are bound by covalent dsp2 hybrid bonds. Such an explanation is acceptable in the case of the transition metals, which readily form dsp2 bonds, but cannot account for the existence of the beryllium compound. It is, however, notable in this connexion that this derivative is conspicuously less stable than the phthalocyanines of the other metals. 

Cartoni et al. [88] studied perspective of the use as stationary phases of n-nonyl- -diketonates of metals such as beryllium (m.p. 53°C), aluminium (m.p. 40°C), nickel (m.p. 48°C) and zinc (liquid at room temperature). These stationary phases show selective retention of alcohols. The retention increases from tertiary to primary alcohols. Alcohols are retained strongly on the beryllium and zinc chelates, but the greatest retention occurs on the nickel chelate. The high retention is due to the fact that the alcohols produce complexes with jS-diketonates of the above metals. Similar results were obtained with the use of di-2-ethylhexyl phosphates with zirconium, cobalt and thorium as stationary phases [89]. 6i et al. [153] used optically active copper(II) complexes as stationary phases for the separation of a-hydroxycarboxylic acid ester enantiomers. Schurig and Weber [158] used manganese(ll)—bis (3-heptafiuorobutyryl-li -camphorate) as a selective stationary phase for the resolution of racemic cycUc ethers by complexation GC. Picker and Sievers [157] proposed lanthanide metal chelates as selective complexing sorbents for GC. Suspensions of complexes in the liquid phase can also be used as stationary phases. Pecsok and Vary [90], for example, showed that suspensions of metal phthalocyanines (e.g., of iron) in a silicone fluid are able to react with volatile ligands. They were used for the separation of hexane-cyclohexane-pentanone and pentane-water-methanol mixtures. 

Beryllium complexes, 3 amines, 7 anionic, 10 hydrates, 6 phthalocyanine, 59 poly carboxylic acid, 33 Schiff bases, 28 Beryllium dichloride ether complexes, 8 Beryllium difluoride ammine complexes, 7 Beryllium dihalides sulfide complexes, 10 Beryllium halides amine complexes, 8 ammonia complexes, 7 carbonyl complexes, 9 Beryllium nitrate basic, 32... 

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