Synthesis and Reduction of Sterically Encumbered Mesoionic Carbene-Stabilized Aryldihaloboranes.
Sterically hindered, in situ generated 1,3,4-substituted 1,2,3-triazol-5-ylidene mesoionic carbenes (MICs) were employed to stabilize a number of aryl- and heteroaryldihaloboranes, as well as the first MIC-supported diborane. Reduction of borane adducts of the 1-(2,6-diisopropylphenyl)-3-methyl-4-tert-butyl-1,2,3-triazol-5-ylidene ligand with KC8in non-coordinating solvents led to intramolecular C-H- and, C-C-activation at an isopropyl residue of the supporting ligand. DFT calculations showed that each of these activation reactions proceeds via a different isomer of a borylene intermediate.
Institute for Sustainable Chemistry & Catalysis with Boron, Julius-Maximilians-Universität Würzburg, Am Hubland, 97074, Würzburg, Germany.|Institute for Inorganic Chemistry, Julius-Maximilians-Universität Würzburg, Am Hubland, 97074, Würzburg, Germany.
Merle
M
Arrowsmith
Institute for Sustainable Chemistry & Catalysis with Boron, Julius-Maximilians-Universität Würzburg, Am Hubland, 97074, Würzburg, Germany.|Institute for Inorganic Chemistry, Julius-Maximilians-Universität Würzburg, Am Hubland, 97074, Würzburg, Germany.
Julian
J
Böhnke
Institute for Sustainable Chemistry & Catalysis with Boron, Julius-Maximilians-Universität Würzburg, Am Hubland, 97074, Würzburg, Germany.|Institute for Inorganic Chemistry, Julius-Maximilians-Universität Würzburg, Am Hubland, 97074, Würzburg, Germany.
Holger
http://orcid.org/0000-0001-9264-1726
H
Braunschweig
Institute for Sustainable Chemistry & Catalysis with Boron, Julius-Maximilians-Universität Würzburg, Am Hubland, 97074, Würzburg, Germany.|Institute for Inorganic Chemistry, Julius-Maximilians-Universität Würzburg, Am Hubland, 97074, Würzburg, Germany.
Haopeng
H
Gao
Institute for Sustainable Chemistry & Catalysis with Boron, Julius-Maximilians-Universität Würzburg, Am Hubland, 97074, Würzburg, Germany.|Institute for Inorganic Chemistry, Julius-Maximilians-Universität Würzburg, Am Hubland, 97074, Würzburg, Germany.
Marc-André
MA
Légaré
Institute for Sustainable Chemistry & Catalysis with Boron, Julius-Maximilians-Universität Würzburg, Am Hubland, 97074, Würzburg, Germany.|Institute for Inorganic Chemistry, Julius-Maximilians-Universität Würzburg, Am Hubland, 97074, Würzburg, Germany.
Valerie
V
Paprocki
Institute for Sustainable Chemistry & Catalysis with Boron, Julius-Maximilians-Universität Würzburg, Am Hubland, 97074, Würzburg, Germany.|Institute for Inorganic Chemistry, Julius-Maximilians-Universität Würzburg, Am Hubland, 97074, Würzburg, Germany.
Jens
J
Seufert
boranes; carbenes; density functional calculations; heterocycles; triazoles