Cooperative and non-cooperative additions involving a silicon atom and a redox-active ligand

Abstract

The silylene [(dpp-bian)Si:] (1), where dpp-bian is 1,2-bis[(2,6-diisopropylphenyl)imino]acenaphthene, exhibits remarkable reactivity with a variety of substrates. It reacts with chloroform and water via O–H and C–Cl bond activation to yield oxidative addition products 2 and 3, respectively. Reactions of 1 with dibenzylideneacetone and tolane involve exclusively the silicon atom and result in [4 + 1]- and [2 + 1]-cycloaddition products 4 and 6. Treatment with isoselenocyanate results in unprecedented cleavage of the CSe bond, leading to activation product 5. In contrast, treatment with acetylene and phenylacetylene leads to cooperative cycloaddition reactions, producing unique cycloadducts 7 and 8. These reactions represent a new type of cycloaddition to a tetravalent silicon atom, facilitated by a redox-active ligand. The new compounds were characterized by NMR and IR spectroscopy, elemental analysis, and X-ray diffraction studies. Their electronic structures and reaction pathways were investigated using DFT calculations.