Abstract
AbstractThe activation of NH3 and CO2 is still an ambitious target for multiply bonded sub‐valent silicon compounds. Now, the precise splitting of the N−H bond of ammonia by (Z)‐imino(silyl)disilene 1 to give trans‐1,2‐adduct 2 a at low temperatures (−78 °C) is presented. According to DFT calculations, the stereospecific hydroamination follows a similar mechanism as the recently reported anti‐addition of H2 to the Si=Si bond of 1. The aminosilane 2 b could also be obtained as the formal silylene addition product under thermodynamic reaction control. By applying low temperatures, the activation of CO2 with 1 selectively afforded the cis‐oxadisilacyclobutanone 7‐c as [2+2] cycloadduct. By performing the reaction directly at ambient temperatures, a mixture of three different‐sized silacycles (4–6) was observed. Their formation was investigated theoretically and their structures were revealed with separate experiments using 1 and the oxygenation agents N2O and O2.
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