Unprecedent formation of methylsilylcarbonates from iridium-catalyzed reduction of CO2 with hydrosilanes

Abstract

The iridium complex [Ir(μ-CF₃SO₃)(κ²-NSi^Me2)₂]₂ (3) (NSi^Me2 = {4-methylpyridine-2-yloxy}dimethylsilyl) has been prepared by reaction of [Ir(μ-Cl)(κ²-NSi^Me2)₂]₂ (1) with two equivalents of AgCF₃SO₃. The solid structure of 3 evidenced its dinuclear nature, being a rare example of an iridium species with triflate groups acting as bridges. The 3-catalyzed reduction of CO₂ with HSiMe(OSiMe₃)₂ affords a mixture of the corresponding silylformate and methoxysilane together with the silylcarbonate CH₃OCO₂SiMe(OSiMe₃)₂ (4a). This is the first time that the formation of silylcarbonates has been observed from the catalytic reduction of CO₂ with silanes. Analogous behaviour has been observed when HSiMe₂Ph and HSiMePh₂ were used as reductants.