@article{KrahfussRadius2021,
  author    = {Krahfuss, Mirjam J. and Radius, Udo},
  title     = {N-Heterocyclic Silylene Main Group Element Chemistry: Adduct Formation, Insertion into E-X Bonds and Cyclization of Organoazides},
  series = {European Journal of Inorganic Chemistry},
  volume    = {2021},
  journal   = {European Journal of Inorganic Chemistry},
  number    = {6},
  doi       = {10.1002/ejic.202000942},
  url       = {http://nbn-resolving.de/urn:nbn:de:bvb:20-opus-224507},
  pages     = {548 -- 561},
  year      = {2021},
  abstract  = {Investigations concerning the reactivity of the N-heterocyclic silylene Dipp\(_{2}\)NHSi (1, 1,3-bis(2,6-diisopropylphenyl)-1,3-diaza-2-silacyclopent-4-en-2-ylidene) towards selected alanes and boranes, elemental halides X\(_{2}\) (X=Br, I), selected halide containing substrates such as tin chlorides and halocarbons, as well as organoazides are presented. The NHSi adducts Dipp\(_{2}\)NHSi⋅AlI\(_{3}\) (2), Dipp\(_{2}\)NHSi⋅Al(C\(_{6}\)F\(_{5}\))\(_{3}\) (3), and Dipp\(_{2}\)NHSi⋅B(C\(_{6}\)F\(_{5}\))\(_{3}\) (4) were formed by the reaction of Dipp\(_{2}\)NHSi with the corresponding Lewis acids AlI\(_{3}\), Al(C\(_{6}\)F\(_{6}\))\(_{3}\) and B(C\(_{6}\)F\(_{5}\))\(_{3}\). Adducts 3 and 4 were tested with respect to their ability to activate small organic molecules, but no frustrated Lewis pair reactivity was observed. Reactions of Dipp\(_{2}\)NHSi with Br\(_{2}\), I\(_{2}\), Ph\(_{2}\)SnCl\(_{2}\) and Me\(_{3}\)SnCl led to formation of Dipp\(_{2}\)NHSiBr\(_{2}\) (5), Dipp\(_{2}\)NHSiI\(_{2}\) (6), Dipp\(_{2}\)NHSiCl\(_{2}\) (7) and {(Me\(_{3}\)Sn)N(Dipp)CH}\(_{2}\) (8), respectively. The reaction with the halocarbons methyl iodide, benzyl chloride, and benzyl bromide afforded the insertion products Dipp\(_{2}\)NHSi(I)(CH\(_{3}\)) (9), Dipp\(_{2}\)NHSi(Cl)(CH\(_{2}\)Ph) (10) and Dipp\(_{2}\)NHSi(Br)(CH\(_{2}\)Ph) (11). Reaction of Dipp\(_{2}\)NHSi with the organoazides Ad-N\(_{3}\) (Ad=adamantyl) and TMS-N\(_{3}\) (TMS=trimethylsilyl) led to the formation of 1-Dipp\(_{2}\)NHSi-2,5-bis(adamantyl)-tetrazoline (12) and bis(trimethylsilyl)amido azido silane (13), respectively. For 2,6-(diphenyl)phenyl-N\(_{3}\) C-H activation occurs and a cyclosilamine 14 was isolated.},
  language  = {en}
}