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

Autor: Lenczyk, Carsten, Roy, Dipak Kumar, Oberdorf, Kai, Nitsch, Jörn, Dewhurst, Rian D., Radacki, Krzysztof, Halet, Jean‐François, Marder, Todd B., Bickelhaupt, Matthias, Braunschweig, Holger
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Zdroj: Chemistry - A European Journal; 12/20/2019, Vol. 25 Issue 72, p16544-16549, 6p
Abstrakt: 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. [ABSTRACT FROM AUTHOR]
Databáze: Complementary Index
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