Hydro-coupling of isocyanates promoted by 1,2-bis(arylimino)acenaphthene aluminum hydrides.

The interaction of aluminum hydrides [(dpp-bian)AlH] (1) and [(Ar-bian)AlH(THF)] (2) (dpp-bian = 1,2-bis[(2,6-diisopropylphenyl)imino]acenaphthene; Ar-bian = 1,2-bis[(2,6-dibenzhydryl-4-methylphenyl)imino]acenaphthene) with isocyanates RNCO (R = Ph, Cy, 3,5-ClPh) proceeds insertion of two molecules of isocyanates into each Al-H bond with the formation of unique Al carboxamides [(Ar-bian)Al{OC(H)N(R)C(NR)O}] (Ar = dpp, R = Ph, 3; Ar = Ar, R = Ph, 4; Ar = Ar, R = Cy, 5; Ar = Ar, R = 3,5-ClCH, 6). In contrast, the reactions of 1 and 2 with an excess of -butylisocyanate afford formimidate derivatives [(Ar-bian)Al{OC(H)N(Bu)}] (Ar = dpp, 7; Ar = Ar, 8). The reactions of ,'-dicyclohexylcarbodiimide with 1 and 2 give [(dpp-bian)Al{(NCy)CH}] (9) and [(Ar-bian)Al(H){(NCy)CH}] (10), correspondingly.

Diversity of transformation of heteroallenes on acenaphthene-1,2-diimine aluminum oxide.

The reactions of oxide [(dpp-bian)Al(μ-O)Al(dpp-bian)] (1) (dpp-bian = 1,2-bis[(2,6-diisopropylphenyl)imino]acenaphthene) with phenyl- or cyclohexylisocyanates result in the formation of carbonimidate derivatives [(dpp-bian)Al(μ-O)(μ-RNCO)Al(dpp-bian)] (R = Ph, 2; Cy, 3). Addition of ,'-dicyclohexylcarbodiimide to compound 1 leads to the formation of ureate complex [(dpp-bian)Al(μ-O)(μ-(CyN)CO)Al(dpp-bian)] (4). The reactions of the oxide 1 with pinacolborane and catecholborane afford oxo-bridged hydride [{(dpp-bian)Al(H)}(μ-O){Al(OBpin)(dpp-bian)}] (5) and compound [{(dpp-bian)Al(OBCat)}(μ-O)] (7), respectively.

Reduction of CO with Aluminum Hydrides Supported with Ar-BIAN Radical-Anions (Ar-BIAN = 1,2-Bis(arylimino)acenaphthene).

The reactions of HAlCl with [(dpp-Bian)Na(EtO)] and [(Ar-Bian)Na(THF)] produce respective aluminum hydrides supported by radical-anionic 1,2-bis(arylimino)acenaphthene ligands, [(dpp-Bian)AlH] ( and [(Ar-Bian)AlH(THF)] () (dpp-Bian = 1,2-bis[(2,6-diisopropylphenyl)imino]acenaphthene); Ar-Bian = 1,2-bis[(2,6-dibenzhydryl-4-methylphenyl)imino]acenaphthene). The reaction of with CO proceeds with reduction of both C═O bonds and results in diolate [{(dpp-Bian)Al(μ-OCH)}] (). Complex reacts with CO to carbonate [{(Ar-Bian)Al(μ-OCHOCO)}] () that is a result of the insertion of CO into the Al-O bond in diolate species formed initially.

Gallium Hydrides with a Radical-Anionic Ligand.

The reaction of ClGaH with a sodium salt of the dpp-Bian radical-anion (dpp-Bian)Na (dpp-Bian = 1,2-bis[(2,6-diisopropylphenyl)imino]acenaphthene) affords paramagnetic gallane (dpp-Bian)Ga(Cl)H (1). Oxidation of (dpp-Bian)Ga-Ga(dpp-Bian) (2) with NO results in the dimeric oxide (dpp-Bian)Ga(μ-O)Ga(dpp-Bian) (3). A treatment of the oxide 3 with phenylsilane affords paramagnetic gallium hydrides (dpp-Bian)GaH (4) and (dpp-Bian)Ga{OSi(Ph)H}H (5) depending on the reagent's stoichiometry.

Unexpected reactivity of an alkylaluminum complex of a non-innocent 1,2-bis[(2,6-diisopropylphenyl)imino]acenaphthene ligand (dpp-bian).

The reaction of (dpp-bian)AlEt(EtO) (1) (dpp-bian = 1,2-bis[(2,6-diisopropylphenyl)imino]acenaphthene) with 4,4'-dimethoxybenzophenone leads to the replacement of EtO with the ketone resulting complex (dpp-bian)AlEt[O[double bond, length as m-dash]C(4-MeOCH)] (2). The reaction of compound 1 with 2,6-di-tert-butyl-4-methylphenol (1 : 1) or PhNH (1 : 1) affords the addition products [dpp-bian(H)]AlEt[O(2,6-tBu-4-MeCH)] (3) and [dpp-bian(H)]AlEt(NPh) (4) correspondingly. Treatment of complex 1 with 0.