Reactivity of the magnesium bisamide complex towards C=C=O-, N=C=O-, and N—N=O-containing substrates

The complex [(dpp-bian)2−Mg2+(THF)3] (1) (dpp-bian is 1,2-bis[(2,6-diisopropylphenyl)imino]acenaphthene) reacts with Ph2C=C=O to form the product of insertion into the Mg—N bond, [(dpp-bian)(Ph2C=C—O)Mg(THF)2] (2), whereas the reaction of 1 with another heteroallene, Ph3SnN=C=O, gives the reduction product [(dpp-bian) Mg(DME)(NCO)]2 (4) and hexaphenyldistannane. Complex 1 reduces Ph2N—N=O, giving [(dpp-bian)MgNPh2(THF)] (3). Complex 2 is the first structurally characterized nucleophilic addition product of ketenes at the Mg—N bond. The new compounds were characterized by IR, EPR, and NMR spectroscopy and elemental analysis. The molecular structures of complexes 2–4 were established by X-ray diffraction.