Aluminum, coordination compounds

Instead of using high-temperature melting to make the precursor alloys, an alternative wet chemistry technique has been proposed where nickel(O) and aluminum coordination compounds are blended together and treated to give nanocrystalline NiAlx alloys with 1 < x < 3 [48], The alloys are leached in the same way as standard skeletal catalysts. Catalysts with higher activity than commercially available Raney nickel have been prepared by this technique, with the activity attributed to the finer structure and homogeneity of the alloys [48,49],... 

It is necessary to pay attention to the fact that, during recent years, the bioinorganic properties of aluminum coordination compounds have become the objects of detailed study their general aspect [354], metabolism and toxicology [355,356], complex formation with nucleozides of di- and triphosphates and nucleo-zide-bound proteins [357], and x-ray analysis of biologically important complexes... 

Aluminum, coordination compounds, 446 Aminopolycarboxylates, lanthanide, complexation, 346-358 Ammine cupric ions, complexity constant determination, 101-106 Ammine cuprous ions, complexity constant determination, 106-107 Ammonium ion-hydrogen-bonding receptor complexes, schematic representation, 150,151/... 

Compounds containing fluorine and chlorine are also donors to BF3. Aqueous fluoroboric acid and the tetrafluoroborates of metals, nonmetals, and organic radicals represent a large class of compounds in which the fluoride ion is coordinating with trifluoroborane. Representative examples of these compounds are given in Table 5. Coordination compounds of boron trifluoride with the chlorides of sodium, aluminum, iron, copper, 2inc, tin, and lead have been indicated (53) they are probably chlorotrifluoroborates. 

Electroplating. Aluminum can be electroplated by the electrolytic reduction of cryoHte, which is trisodium aluminum hexafluoride [13775-53-6] Na AlE, containing alumina. Brass (see COPPERALLOYS) can be electroplated from aqueous cyanide solutions which contain cyano complexes of zinc(II) and copper(I). The soft CN stabilizes the copper as copper(I) and the two cyano complexes have comparable potentials. Without CN the potentials of aqueous zinc(II) and copper(I), as weU as those of zinc(II) and copper(II), are over one volt apart thus only the copper plates out. Careful control of concentration and pH also enables brass to be deposited from solutions of citrate and tartrate. The noble metals are often plated from solutions in which coordination compounds help provide fine, even deposits (see Electroplating). 

Beryllium, calcium, boron, and aluminum act in a similar manner. Malonic acid is made from monochloroacetic acid by reaction with potassium cyanide followed by hydrolysis. The acid and the intermediate cyanoacetic acid are used for the synthesis of polymethine dyes, synthetic caffeine, and for the manufacture of diethyl malonate, which is used in the synthesis of barbiturates. Most metals dissolve in aqueous potassium cyanide solutions in the presence of oxygen to form complex cyanides (see Coordination compounds). 

Selenoaldehydes 104, like thioaldehydes, have also been generated in situ from acetals and then directly trapped with dienes, thus offering a useful one-pot procedure for preparing cyclic seleno-compounds [103,104], The construction of a carbon-selenium double bond was achieved by reacting acetal derivatives with dimethylaluminum selenide (Equation 2.30). Cycloadditions of seleno aldehydes occur even at 0 °C. In these reactions, however, the carbon-selenium bond formed by the nucleophilic attack of the electronegative selenium atom in 105 to the aluminum-coordinated acetal carbon, may require a high reaction temperature [103], The cycloaddition with cyclopentadiene preferentially gave the kinetically favorable endo isomer. 

One of the more important recent developments in organometallic aluminum chemistry has been the formation and isolation of low-coordinate compounds, and, in particular, cations. These were first prepared in reactions of various aluminum reagents with crown ethers to form the inclusion compounds known as liquid clathrates. 71,72 Most of the evidence supports the presence of ion pairs as the basis of the solvent inclusion effect. Indeed, the compound [AlMe2-18-crown-6]+[AlMe2Cl2] was isolated from one such system (the cation is shown in Figure 6(a)).73 This was the first time the Me2Al+ unit had been structurally characterized. 

Another example of a Bill compound is offered by the ligand VAPOL ( vaulted bisphenanthrol), which combines with AICI3 to form a three-coordinate complex, with no dative interactions. This compound will catalyze Diels-Alder reactions [64]. A five-coordinate compound, with two dative carbonyl bonds attached to the aluminum, has been postulated as the active intermediate in the catalytic reaction. 

Equation (3)]. Polymerization of PO also proceeds rapidly to give the low molecular weight PPO [J/n = 4050 g mol— 1.2]. Since the molecular weight of polymer indicates that less than 10% of aluminum sites are active for producing the polymer, an oligomeric aluminum complex is supposed to be an active species although the characterization is not fully achieved. In this system, exclusion of a coordinated compound such as THE is essential for the high catalytic activities. Thus, aluminum complex prepared by the reaction of APBus and methylphosphonic acid in the presence of THE exhibits much less catalytic activity. 

Pyridine readily forms stable coordination compounds. Thus, boron, aluminum and gallium trihalides react at 0°C in an inert solvent to give 1 1 adducts (cf. 85). Steric factors are important, and a-substituents decrease the ease of reaction. This is illustrated by the heats of reaction of pyridine, 2-methylpyridine and 2,6-dimethylpyridine with boron trifluoride which are 101.3, 94.1 and 73.2 kJ mol-1, respectively. The marked decrease in exothermicity here should be contrasted with the small steric requirement of the proton as shown by the pA., values of substituted pyridines (see Section 3.2.1.3.4). 

Different historians ascribe different dates to the discovery of the first coordination compound. Perhaps the earliest known of all coordination compounds is the bright-red alizarin dye, a calcium aluminum chelate compound of hydroxyanthraquinone. It was first used in India and known to the ancient Persians and Egyptians long before it was used by the Greeks and Romans. Joseph s coat of many colors may possibly have been treated with it. 

Enantiomer-selective polymerization of MBMA has also been attained by using the reaction products of chiral amine compounds, 168 and 169, with cyclohexylmagnesium bromide as initiator [242,243] and by using the aluminum porphyrin complex 170 in the presence of optically active aluminum alkoxide compounds 171a-e [244], In the latter systems, the enantiomer selection is based on enantiomer-selective coordination of the chiral aluminum compounds to MBMA as revealed by NMR analysis. With 171e as a catalyst, the ee of the unreacted monomer is 40% at 75% monomer conversion ratio in the polymerization at -70°C. 

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