Uncatalyzed Hydrogenation of First-Row Main Group Multiple Bonds

Merle Arrowsmith; Julian Böhnke; Holger Braunschweig; Mehmet Ali Celik; Theresa Dellermann; Kai Hammond

doi:10.1002/chem.201604094

Uncatalyzed Hydrogenation of First-Row Main Group Multiple Bonds

Chemistry. 2016 Nov 21;22(48):17169-17172. doi: 10.1002/chem.201604094. Epub 2016 Oct 25.

Authors

Merle Arrowsmith^{1

2}, Julian Böhnke^{1

2}, Holger Braunschweig^{1

2}, Mehmet Ali Celik^{1

2}, Theresa Dellermann^{1

2}, Kai Hammond^{1

2}

Affiliations

¹ Institute for Inorganic Chemistry, Julius-Maximilians-Universität Würzburg, Am Hubland, 97074, Würzburg, Germany.
² Institute for Sustainable Chemistry & Catalysis with Boron, Julius-Maximilians-Universität Würzburg, Am Hubland, 97074, Würzburg, Germany.

PMID: 27685839
DOI: 10.1002/chem.201604094

Abstract

Room temperature hydrogenation of an SIDep-stabilized diboryne (SIDep=1,3-bis(diethylphenyl)-4,5-dihydroimidazol-2-ylidene) and a cAAC-supported diboracumulene (cAAC=1-(2,6-diisopropylphenyl)-3,3,5,5-tetramethylpyrrolidin-2-ylidene) provided the first selective route to the corresponding 1,2-dihydrodiborenes. DFT calculations showed an overall exothermic (ΔG=19.4 kcal mol^-1 ) two-step asynchronous H₂ addition mechanism proceeding via a bridging hydride.

Keywords: carbenes; diborenes; hydrogenation; main-group chemistry; reaction mechanism.