The Renaissance of Aluminum Chemistry

Abstract

The preparation and reactions of stable monomeric and tetrameric organoaluminum(I) compounds are described. Especially, their conversion to the more stable oxidation state (III) is discussed. The synthesis of unusual and unique molecules such as LAl(OH)(2), LAl(SH)(2), LAl(SeH)(2), and LAl(NH(2))(2) is reported. A new synthetic approach to organometallic hydroxides and amides was discovered, when N-heterocyclic carbenes are used as hydrogen chloride acceptors. The synthesis of LGeOH demonstrates that this method can also be applied for other elements in the periodic system. The successful preparation of carbaalanes and aluminum nitride clusters resulted in the generation of several model compounds for the fixation of organometal substituents on carbide and nitride surfaces. It is shown that AlH(3).NMe(3) is a powerful hydroalumination reagent for acetylenes, nitriles, and isonitriles.

Synthesis and Characterization of Copper(I) Halide Complexes with N‐(2, 6‐Diisopropylphenyl)‐N′‐benzoylthiourea: Monomeric, Dimeric, and Cage Structures

“…[14] Starting from the basic molecule of N-aryl-NЈ-benzoylthiourea, a number of derivatives have been synthesized and structurally characterized with varying aryl rings typically modified by methyl, [15] carboxyl, [16] phenyl, [17] hydroxyl, [18] trifluoromethyl, [19] ferrocenoyl, [10,20] and halide [21] substituents. However, the isopropyl group, which has been used as a bulky group in a number of ligand systems, [22] was not so common in acylthiourea derivatives. [12] Previous work with β-diketiminato ligands has shown that the substituent effect on the synthesis of dialuminoxanes is of principal importance.…”

Hydroalumination of diazo and azido compounds: An Al-H addition to end-on nitrogen of substrates

“…It exhibits diverse reactivity patterns with the variation of aluminum hydrides as well as its interacted substrate sources [1][2][3][4][5][6][7], and thus attracts particular interest. The use of AlH 3 ·NMe 3 or dialkylaluminum hydrides as precursors to react with unsaturated molecules, such as alkynes [8][9][10][11][12][13], nitriles, and isonitriles [14][15][16][17], has led to the formation of unique classes of carbaalane, imidoalane, and carbaamidoalane clusters. Several different reaction mechanisms have been suggested and discussed with respect to the highly aggregated forms of the hydroalumination products.…”

“…In contrast to the formation of highly aggregated alane clusters using simple aluminum hydrides [8][9][10][11][12][13][14][15][16][17], such lower aggregation products are available when the reactive aluminum hydrides are stabilized by the sterically demanding ligands [19,20]. This may offer a better understanding on the reaction pathways and further the interaction mechanisms.…”

Fluorine functionalized compounds of group 13 elements

“…Aluminum compounds with Al in the formal oxidation state (+3) are Lewis acids [27] whereas Al in oxidation state (+1) has a dual behaviour and can act as a Lewis base and Lewis acid [28][29][30]. This property of the latter compound has been postulated based on the results of the ab initio calculations on the [LAl] species [31] [L = HC{(CMe)(2,6-iPr 2 C 6 H 3 N)} 2 ].…”