Steric Effects Dictate the Formation of Terminal Arylborylene Complexes of Ruthenium from Dihydroboranes

Carsten Lenczyk, Dipak Kumar Roy, Jörn Nitsch, Krzysztof Radacki, Florian Rauch, Rian D. Dewhurst, F. Matthias Bickelhaupt, Todd B. Marder, Holger Braunschweig*

*Corresponding author for this work

Research output: Contribution to JournalArticleAcademicpeer-review

Abstract

The steric and electronic properties of aryl substituents in monoaryl borohydrides (Li[ArBH3]) 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.

Original languageEnglish
Pages (from-to)13566-13571
Number of pages6
JournalChemistry - A European Journal
Volume25
Issue number59
Early online date21 Aug 2019
DOIs
Publication statusPublished - 22 Oct 2019

Funding

H.B. and T.B.M. gratefully acknowledge financial support from the Deutsche Forschungsgemeinschaft. D.K.R. is grateful for a postdoctoral fellowship from the Science and Engineering Research Board (Award no. SB/OS/PDF-052/2016-17) of India. F.M.B. thanks the Netherlands Organization for Scientific Research (NWO) for financial support. The authors also thank Dr. Sylviane Sabo-Etienne for helpful discussions.

FundersFunder number
Netherlands Organization for Scientific Research
Deutsche Forschungsgemeinschaft
Science and Engineering Research BoardSB/OS/PDF-052/2016-17
Nederlandse Organisatie voor Wetenschappelijk Onderzoek

    Keywords

    • boranes
    • borohydrides
    • borylenes
    • sigma boranes
    • steric effects

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