TY - INPR A1 - Auerhammer, Dominic A1 - Arrowsmith, Merle A1 - Böhnke, Julian A1 - Braunschweig, Holger A1 - Dewhurst, Rian D. A1 - Kupfer, Thomas T1 - Brothers from Another Mother: a Borylene and its Dimer are Non-Interconvertible but Connected through Reactivity T2 - Chemical Science N2 - The self-stabilizing, tetrameric cyanoborylene [(cAAC)B(CN)]4 (I, cAAC = 1-(2,6-diisopropylphenyl)-3,3,5,5-tetramethylpyrrolidin-2-ylidene) and its diborene relative, [(cAAC)(CN)B=B(CN)(cAAC)] (II), both react with disulfides and diselenides to yield the corresponding cAAC-supported cyanoboron bis(chalcogenides). Furthermore, reactions of I or II with elemental sulfur and selenium in various stoichiometries provided access to a variety of cAAC- stabilized cyanoboron-chalcogen heterocycles, including a unique dithiaborirane, a diboraselenirane, 1,3-dichalcogena-2,4-diboretanes, 1,3,4-trichalcogena- 2,5-diborolanes and a rare six-membered 1,2,4,5-tetrathia-3,6-diborinane. Stepwise addition reactions and solution stability studies provided insights into the mechanism of these reactions and the subtle differences in reactivity observed between I and II. KW - borylenes KW - diborenes KW - boron KW - carbenes KW - chalcogens Y1 - 2018 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:bvb:20-opus-157125 ER - TY - JOUR A1 - Lenczyk, Carsten A1 - Roy, Dipak Kumar A1 - Nitsch, Jörn A1 - Radacki, Krzysztof A1 - Rauch, Florian A1 - Dewhurst, Rian D. A1 - Bickelhaupt, F. Matthias A1 - Marder, Todd B. A1 - Braunschweig, Holger T1 - Steric Effects Dictate the Formation of Terminal Arylborylene Complexes of Ruthenium from Dihydroboranes JF - Chemistry - A European Journal N2 - The steric and electronic properties of aryl substituents in monoaryl borohydrides (Li[ArBH\(_3\)]) and dihydroboranes were systematically varied and their reactions with [Ru(PCy\(_3\))\(_2\)HCl(H\(_2\))] (Cy: cyclohexyl) were studied, resulting in bis(σ)‐borane or terminal borylene complexes of ruthenium. These variations allowed for the investigation of the factors involved in the activation of dihydroboranes in the synthesis of terminal borylene complexes. The complexes were studied by multinuclear NMR spectroscopy, mass spectrometry, X‐ray diffraction analysis, and density functional theory (DFT) calculations. The experimental and computational results suggest that the ortho‐substitution of the aryl groups is necessary for the formation of terminal borylene complexes. KW - Arylborylene Complexes KW - Ruthenium KW - Dihydroboranes KW - boranes KW - borohydrides KW - borylenes KW - steric effects KW - sigma boranes Y1 - 2019 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:bvb:20-opus-219537 SN - 1521-3765 VL - 25 IS - 59 ER -