Addition of nitriles to alkaline earth metal complexes of 1,2-bis[(phenyl)imino]acenaphthenes

Compounds [Sr(dpp-bian)(thf)(4)] (2), [Ba(dpp-bian)(dMe)(2.5)] (3) and [Mg(dtb-bian)(thf)(2)] (4) (dpp-bian = 1,2-bis[(2,6-diisopropylphenyl)imino]acenaphthene; dtb-bian = 1,2bisf[(2,5-di-tert-butylphenyl)imino]ace-naphthene) were prepared by reduction of dpp-bian and dtb-bian with an excess of metallic Mg, Sr, or Ba in THIF or DME. Reactions of (Mg(dpp-bian)(thf)(3)] 3, and 4 with diphenylace-tonitrile gave keteniminates [Mg(dpp-bianH)(NCCPh2)(thf)2] (5), [Mg(dtb-bianH)(NCCPh2)(thf)(2)] (6), and [Ba(dpp-bianH)(NCCPh2)(dme)(2)] (7), respectively. The reaction of 2 with CH3C=-N in THIF gave [{Sr(dpp-bianH)[N(H)C(CH3)C(H)CN](thf)}(2)] (8). The compounds 2, 3, 5-8 were characterized by elemental analysis, and IR and NMR spectroscopy. Molecular structures of 2, 3, 7, and 8 were determined by single-crystal X-ray diffraction. In contrast to reactions of alkali-metal reagents, magnesium amides, or yttriumalkyls with alpha-H acidic nitriles, which are accompanied by an amine or an alkane elimination, the reactions of [Mg(dpp-bian)(thf)(3)] (1), 2, 3, and 4 with such nitriles proceeded with formation of Mg, Sr, and Ba keteniminates and simultaneous protonation of one nitrogen atom of the bian ligand. The NMR spectroscopic data obtained for complex 5 indicated that in solution the amino hydrogen atom underwent the fast (on the NMR timescale) shuttle transfer between both nitrogen atoms of the dpp-bianH ligand.