@article{RamlerSchwarzmannStoyetal.2022,
  author    = {Ramler, Jacqueline and Schwarzmann, Johannes and Stoy, Andreas and Lichtenberg, Crispin},
  title     = {Two Faces of the Bi-O Bond: Photochemically and Thermally Induced Dehydrocoupling for Si-O Bond Formation},
  series = {European Journal of Inorganic Chemistry},
  volume    = {2022},
  journal   = {European Journal of Inorganic Chemistry},
  number    = {7},
  doi       = {10.1002/ejic.202100934},
  url       = {http://nbn-resolving.de/urn:nbn:de:bvb:20-opus-257428},
  year      = {2022},
  abstract  = {The diorgano(bismuth)alcoholate [Bi((C\(_{6}\)H\(_{4}\)CH\(_{2}\))\(_{2}\)S)OPh] (1-OPh) has been synthesized and fully characterized. Stoichiometric reactions, UV/Vis spectroscopy, and (TD-)DFT calculations suggest its susceptibility to homolytic and heterolytic Bi-O bond cleavage under given reaction conditions. Using the dehydrocoupling of silanes with either TEMPO or phenol as model reactions, the catalytic competency of 1-OPh has been investigated (TEMPO=(tetramethyl-piperidin-1-yl)-oxyl). Different reaction pathways can deliberately be addressed by applying photochemical or thermal reaction conditions and by choosing radical or closed-shell substrates (TEMPO vs. phenol). Applied analytical techniques include NMR, UV/Vis, and EPR spectroscopy, mass spectrometry, single-crystal X-ray diffraction analysis, and (TD)-DFT calculations.},
  language  = {en}
}
@article{OberdorfHanftRamleretal.2021,
  author    = {Oberdorf, Kai and Hanft, Anna and Ramler, Jacqueline and Krummenacher, Ivo and Bickelhaupt, Matthias and Poater, Jordi and Lichtenberg, Crispin},
  title     = {Bismuth Amides Mediate Facile and Highly Selective Pn-Pn Radical-Coupling Reactions (Pn=N, P, As)},
  series = {Angewandte Chemie, International Edition},
  volume    = {60},
  journal   = {Angewandte Chemie, International Edition},
  number    = {12},
  doi       = {10.1002/anie.202015514},
  url       = {http://nbn-resolving.de/urn:nbn:de:bvb:20-opus-236582},
  pages     = {6441-6445},
  year      = {2021},
  abstract  = {The controlled release of well-defined radical species under mild conditions for subsequent use in selective reactions is an important and challenging task in synthetic chemistry. We show here that simple bismuth amide species [Bi(NAr\(_2\))\(_3\)] readily release aminyl radicals [NAr\(_2\)]. at ambient temperature in solution. These reactions yield the corresponding hydrazines, Ar\(_2\)N-NAr\(_2\), as a result of highly selective N-N coupling. The exploitation of facile homolytic Bi-Pn bond cleavage for Pn-Pn bond formation was extended to higher homologues of the pnictogens (Pn=N-As): homoleptic bismuth amides mediate the highly selective dehydrocoupling of HPnR\(_2\) to give R\(_2\)Pn-PnR\(_2\). Analyses by NMR and EPR spectroscopy, single-crystal X-ray diffraction, and DFT calculations reveal low Bi-N homolytic bond-dissociation energies, suggest radical coupling in the coordination sphere of bismuth, and reveal electronic and steric parameters as effective tools to control these reactions.},
  language  = {en}
}