Aluminum complexes structure

U.S. 5,466,392 Organic electroluminescence device and compound having an aluminum complex structure... 

The first example of a neutral aluminum complex of diazaphosphane, the 1,3,2,4-diazaphosphaluminetidine 50, Eq. (4), has been synthesized by the dehydrogenation reaction between Lewis acid-base adduct H3AI <— NMca and fBuP[N(H)fBu 2 49. The product fBuP(NfBu)2(H)Al [Pg.111]

Yu et al. synthesized two methyl-substituted Alq3, named tris(2,3-dimethyl-8-hydroxy-quinoline) aluminum complex (Alm23q3, 237) (Scheme 3.72) [264]. This compound emits blue color with an emission peak centered at 470 nm and FWHM of 90 nm. OLEDs with a structure of ITO/TPD/Alm23q3/Mg Ag emit blue light and the luminous efficiency is 0.62 lm/W with a maximum luminance of 5400 cd/m2 at 19 V. 

In the presence of an aluminum reagent, 2,3-butadienyltrimethylsilane can also accept the intramolecular electrophilic attack of the ketone-aluminum complex to afford bicyclic products via intermediate 60 [31]. The structures of the products depend on the aluminum reagent used [31]. 

Corey and colleagues215 prepared chiral aluminum complexes from chiral bis(sulfona-mides) and trimethylaluminum. These were successfully applied in the cycloadditions of 3-acryloyl-l,3-oxazolidin-2-one (17a) with substituted cyclopentadienes. Thus, the reaction of 3-acryloyl-l,3-oxazolidin-2-one with 5-(benzyloxymethyl)cyclopentadiene (331) afforded 332 with 94% ee (equation 93). A transition state was proposed based on the X-ray structure of the chiral catalyst and on NMR data of the 1 1 complex between 333... 

Its molecular structure (Figure 37) consists of a centrosymmetric dimer with a bridging H2Al(OR)( U-OR)2Al(OR)H2 entity. The Ta atoms are approximately square pyramidal, with the four phosphorus atoms forming the basal plane (Ta lies 0.64 A out of it). The relatively short Ta—A1 distances are comparable to those found in other transition metal aluminum complexes (Ta—Al 2.79-3.13 A). The hydrogen atoms have not been located, but were evidenced by chemical and spectroscopic techniques (IR 1605, 1540 cm 1 HNMR 16.30p.p.m.). The Ta—(ju-H2)A1 unit is relatively stable, and (54) is inert to carbon monoxide or trimethylamine. It is a poor catalyst in the isomerization of 1-pentene. Formation of complexes analogous to (54) may explain the low yields often obtained from alkoxoaluminohy-drides and metal halides. 

A more complex structure 0 is that of PuAl. This crystal is based on the sequence of hexagonal layers cckcchcch --, each layer containing plutonium atoms and aluminum atoms in the J ratio. 

These spontaneously formed species cannot be isolated (/56) hence they have only been identified spectroscopically (34, 157, 158). Henrici-Olive and Olive (159) suggested that soluble titanium-aluminum complexes have an octahedral structure relative to the coordination sphere of the titanium atoms. However, subsequent research (160) showed that, at least for the primarily formed complexes, there is no octahedral structure present. It is most likely that there is a tetrahedral structure for the titanium, in accordance with the 1959 proposal of Breslow and Newburg (127). 

Fifty-six years ago the very first siderophore, mycobactin, was isolated by the crystallization of the aluminum complex. Mycobactins from Gram-positive Mycobacteria and the closely related nocobactins from Nocardia embody a series of lipid-soluble siderophores located in the lipid-rich boundary layers of these bacteria (Figure 2(c)). The X-ray structure revealed that iron binding in mycobactins is accomplished by two hydroxamates, a phenolate group, and oxazoline nitrogen. 

The crystal structures of all complex aluminum hydrides are built up by [AlH4] tetrahedra or [AlHg] octahedral units. These building units can be either isolated, as for example in NaAlH4, or they can form more complex structures such as chainlike structures, as for CaAlHs. The decomposition of alkaline earth aluminum hydrides proceeds via hydrides to intermetallic compounds whereas alkali metal alanates decompose via an intermediate hexahydride structure to the corresponding hydride. Table 5.2 summarizes the physical data of selected complex aluminum hydrides. 

Boron s chemistry is so different from that of the other elements in this group that it deserves separate discussion. Chemically, boron is a nonmetal in its tendency to form covalent bonds, it shares more similarities with carbon and silicon than with aluminum and the other Group 13 elements. Like carbon, boron forms many hydrides like silicon, it forms oxygen-containing minerals with complex structures (borates). Compounds of boron have been used since ancient times in the preparation of glazes and borosilicate glasses, but the element itself has proven extremely difficult to purify. The pure element has a wide diversity of allotropes (different forms of the pure element), many of which are based on the icosahedral Bj2 unit. 

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