Toward Transition-Metal-Templated Construction of Arylated B4 Chains by Dihydroborane Dehydrocoupling

Carsten Lenczyk, Dipak Kumar Roy, Kai Oberdorf, Jörn Nitsch, Rian D. Dewhurst, Krzysztof Radacki, Jean François Halet*, Todd B. Marder, Matthias Bickelhaupt, Holger Braunschweig

*Corresponding author for this work

Research output: Contribution to JournalArticleAcademicpeer-review


The reactivity of a diruthenium tetrahydride complex towards three selected dihydroboranes was investigated. The use of [DurBH2] (Dur=2,3,5,6-Me4C6H) and [(Me3Si)2NBH2] led to the formation of bridging borylene complexes of the form [(Cp*RuH)2BR] (Cp*=C5Me5; 1 a: R=Dur; 1 b: R=N(SiMe3)2) through oxidative addition of the B−H bonds with concomitant hydrogen liberation. Employing the more electron-deficient dihydroborane [3,5-(CF3)2-C6H3BH2] led to the formation of an anionic complex bearing a tetraarylated chain of four boron atoms, namely Li(THF)4[(Cp*Ru)2B4H5(3,5-(CF3)2C6H3)4] (4), through an unusual, incomplete threefold dehydrocoupling process. A comparative theoretical investigation of the bonding in a simplified model of 4 and the analogous complex nido-[1,2(Cp*Ru)2(μ-H)B4H9] (I) indicates that there appear to be no classical σ-bonds between the boron atoms in complex I, whereas in the case of 4 the B4 chain better resembles a network of three B−B σ bonds, the central bond being significantly weaker than the other two.

Original languageEnglish
Pages (from-to)16544-16549
Number of pages6
JournalChemistry - A European Journal
Issue number72
Publication statusPublished - 20 Dec 2019


  • boron
  • B−H activation
  • dehydrocoupling
  • ruthenium
  • transition metal


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