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The metathesis reaction of aluminum(III) dihydride LAlH 2 (1) (L = (ArNCMe) 2 CH, Ar = 2,6-i-Pr 2 C 6 H 4 ) with n-BuLi and n-Bu 2 Mg, respectively, resulted in di-n-butyl aluminum complex LAl(n-Bu) 2 (2). Meanwhile 1 reacted with MeLi producing dimethyl aluminum LAlMe 2 (3). Complexes 2 and 3 were characterized by NMR and elemental analysis, and 2 was additionally studied by single-crystal X-ray diffraction. The reported synthesis allows for access of dialkylaluminum complexes from aluminum-(III) dihydride compound (1) with excellent yields. The chemoselective double hydroboration of nitriles or single hydroboration of carbodiimides was studied with pinacolborane (HBpin) using LAl(n-Bu) 2 (2) as the precatalyst to afford bis(boryl)amines (4a−4m) and N-borylamines (6a− 6d) under solvent-free and mild conditions (60 °C). The records show that the catalytic reactions proceed in quantitative yields and short time. Moreover, nearly quantitative yield of di(boryl)(silyl)amine ( 5) was obtained, when cyanobenzene was reacted with equal amounts of HBpin and phenylsilane in the presence of precatalsyt 2. A comparison of the previously reported hydroboration reactions with nitriles in the literature and our results in the presence of the precatalyst LAl(n-Bu) 2 show convincingly the better results of short reaction time, mild reaction conditions, and quantitative yields.

The silicon atom in LSiCl or LSiMes (L = PhC­(NtBu)2, Mes = 2,4,6-Me3C6H2) inserts into the B–X bond of RBX2 (R = Ph, Mes, N­(SiMe3)2; X = Cl, Br), which is followed by the migration of the amidinate ligand and the halide atom. By this way, LB­(R)­SiCl3 (R = Ph, 2; Mes, 3; N­(SiMe3)2, 4) and LB­(R)­SiX2Mes (R = Ph, X = Cl, 5; R = Mes, X = Cl, 6; R = Mes, X = Br, 7) were obtained. Furthermore, a silylene–borane adduct LClSi → BPhCl2 (1) was obtained as an intermediate in the formation of compound 2. Compounds 2–7 are rare examples of borylhalosilanes.

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A simple and efficient catalytic system for Na2PdCl4 catalyzing the Suzuki‐Miyaura reaction of dibromobenzene and arylboronic acid has been developed by using 2N2O‐salen as a ligand in H2O/EtOH (V:V=4:1) at 100°C. Using this method, the reactions of substrates containing sterically demanding ortho substituents (e.g. dibromobenzene and/or arylboronic acids) proceeded efficiently, with the corresponding terphenyl derivatives being produced in moderate to excellent yields. Furthermore, this method offers interesting features for the multi‐gram scale synthesis of terphenyl compound.

Seven novel aluminium complexes supported by Schiff base ligands derived from o‐diaminobenzene or o‐aminothiophenol were synthesized and characterized. The reactions of AlMe3 with L1 (N,N′‐bis(benzylidine)‐o‐phenylenediamine) and L2 (N,N′‐bis(2‐thienylmethylene)‐o‐phenylenediamine) gave the complexes L1AlMe3 (1) and L2AlMe2 (2), respectively, which involved two types of reaction mechanisms: one was proton transfer and ring closure, and the other was alkyl transfer. Complexes L3AlMe2 (HL3 = 4‐chlorobenzylidene‐o‐aminothiophenol) (3), L4AlMe2 (HL4 = 2‐thiophenecarboxaldehyde‐o‐aminothiophenol) (4), L3AlH(NMe3) (5), L4AlH(NMe3) (6) and L5AlH(NMe3) (HL5 = 4‐methylbenzylidene‐o‐aminothiophenol) (7) were prepared by reacting HL3–5 with equimolar AlMe3 or H3Al⋅NMe3, respectively. Compounds 3–7 feature an organic–inorganic hybrid containing CNAlSC five‐membered ring. All complexes were characterized using 1H NMR and 13C NMR spectroscopy, X‐ray crystal structure analysis and elemental analysis. The efficient catalytic performances of 1–7 for the hydroboration of carbonyl groups were investigated, with compound 4 exhibiting the highest catalytic activity among all the complexes.