Precise Activation of Ammonia and Carbon Dioxide by an Iminodisilene

Daniel Wendel, Tibor Szilvási, Daniel Henschel, Philipp J. Altmann, Christian Jandl, Shigeyoshi Inoue, Bernhard Rieger

Research output: Contribution to journalArticlepeer-review

51 Scopus citations

Abstract

The 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.

Original languageEnglish
Pages (from-to)14575-14579
Number of pages5
JournalAngewandte Chemie International Edition in English
Volume57
Issue number44
DOIs
StatePublished - 26 Oct 2018

Keywords

  • carbon dioxide fixation
  • main group elements
  • oxygenation
  • silicon
  • subvalent compounds

Fingerprint

Dive into the research topics of 'Precise Activation of Ammonia and Carbon Dioxide by an Iminodisilene'. Together they form a unique fingerprint.

Cite this