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-Cl Ph) 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-Cl C H , 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. New compounds 3-10 have been characterized by ESR spectroscopy; their molecular structures have been established by single-crystal X-ray analysis.