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Steric Effects Dictate the Formation of Terminal Arylborylene Complexes of Ruthenium from Dihydroboranes |
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| Authors: | Dr Carsten Lenczyk Dr Dipak Kumar Roy Dr Jörn Nitsch Dr Krzysztof Radacki Florian Rauch Dr Rian D Dewhurst Prof Dr F Matthias Bickelhaupt Prof Dr Todd B Marder Prof Dr Holger Braunschweig |
| Institution: | 1. Institute for Inorganic Chemistry, Julius-Maximilians-Universität Würzburg, Am Hubland, 97074, Würzburg (Germany), and Institute for Sustainable Chemistry & Catalysis with Boron, Julius-Maximilians-Universität Würzburg, Am Hubland, 97074 Würzburg, Germany;2. Institute for Inorganic Chemistry, Julius-Maximilians-Universität Würzburg, Am Hubland, 97074, Würzburg (Germany), and Institute for Sustainable Chemistry & Catalysis with Boron, Julius-Maximilians-Universität Würzburg, Am Hubland, 97074 Würzburg, Germany
Discipline of Chemistry, Indian Institute of Technology Indore, Khandwa Road, Simrol, Indore, 453552, M.P. India;3. Department of Theoretical Chemistry and Amsterdam Center for Multiscale Modeling (ACMM), Vrije Universiteit Amsterdam, De Boelelaan 1083, 1081 HV Amsterdam, (The Netherlands), and Institute for Molecules and Materials (IMM), Radboud University, Heyendaalseweg 135, 6525 AJ, Nijmegen, The Netherlands |
| Abstract: | The steric and electronic properties of aryl substituents in monoaryl borohydrides (LiArBH3]) and dihydroboranes were systematically varied and their reactions with Ru(PCy3)2HCl(H2)] (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. |
| Keywords: | boranes borohydrides borylenes steric effects sigma boranes |