Synthesis and reactivity of the complexes [(dpp-bian)SiCl 2 ] and [(dpp-bian)Si{FeCp(CO)} 2 (μ-CO)] (dpp-bian is 1,2-bis[(2,6-diisopropylphenyl)imino]acenaphthene)

The complex [(dpp-bian)SiCl 2 ] ( 1 ) was synthesized by the reaction of the free 1,2-bis[(2,6-diisopropylphenyl)imino]acenaphthene (dpp-bian) ligand with Si 2 Cl 6 . Despite the presence of the dpp-bian dianion, complex 1 is inert toward heteroallenes. An attempt to increase the reactivity of complex 1 by abstracting a halogen atom from [(dpp-bian)-SiCl 2 ] by the treatment with AlCl 3 led to the formation of the cationic complex [(dpp-bian)SiCl 2 ][Al 2 Cl 7 ] ( 2 ). The iron μ-silylene complex [(dpp-bian)Si{FeCp(CO)} 2 (μ-CO)] ( 4 ) was synthesized by the reaction of silylene [(dpp-bian)Si] ( 3 ) with 0.5 mol. equiv. of [CpFe(CO) 2 ] 2 . The reaction of 4 with phenyl isothiocyanate afforded sulfide [(dpp-bian)-SiS] 2 ( 5 ). The new compounds were characterized by IR ( 2, 4, 5 ), EPR ( 2 ), and multi-nuclear NMR ( 4 ) spectroscopy and by elemental analysis. The molecular structures of complexes 2, 4 , and 5 were established by X-ray diffraction.