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Toward Transition‐Metal‐Templated Construction of Arylated B\(_{4}\) Chains by Dihydroborane Dehydrocoupling

Please always quote using this URN: urn:nbn:de:bvb:20-opus-214324
  • The reactivity of a diruthenium tetrahydride complex towards three selected dihydroboranes was investigated. The use of [DurBH\(_{2}\)] (Dur=2,3,5,6‐Me\(_{4}\)C\(_{6}\)H) and [(Me\(_{3}\)Si)\(_{2}\)NBH\(_{2}\)] led to the formation of bridging borylene complexes of the form [(Cp\(^{*}\)RuH)\(_{2}\)BR] (Cp\(^{*}\)=C\(_{5}\)Me\(_{5}\); 1 a: R=Dur; 1 b: R=N(SiMe\(_{3}\))\(_{2}\)) through oxidative addition of the B−H bonds with concomitant hydrogen liberation. Employing the more electron‐deficient dihydroboraneThe reactivity of a diruthenium tetrahydride complex towards three selected dihydroboranes was investigated. The use of [DurBH\(_{2}\)] (Dur=2,3,5,6‐Me\(_{4}\)C\(_{6}\)H) and [(Me\(_{3}\)Si)\(_{2}\)NBH\(_{2}\)] led to the formation of bridging borylene complexes of the form [(Cp\(^{*}\)RuH)\(_{2}\)BR] (Cp\(^{*}\)=C\(_{5}\)Me\(_{5}\); 1 a: R=Dur; 1 b: R=N(SiMe\(_{3}\))\(_{2}\)) through oxidative addition of the B−H bonds with concomitant hydrogen liberation. Employing the more electron‐deficient dihydroborane [3,5‐(CF\(_{3}\))\(_{2}\)‐C\(_{6}\)H\(_{3}\)BH\(_{2}\)] led to the formation of an anionic complex bearing a tetraarylated chain of four boron atoms, namely Li(THF)\(_{4}\)[(Cp\(^{*}\)Ru)\(_{2}\)B\(_{4}\)H\(_{5}\)(3,5‐(CF\(_{3}\))\(_{2}\)C\(_{6}\)H\(_{3}\))\(_{4}\)] (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)B\(_{4}\)H\(_{9}\)] (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 B\(_{4}\) chain better resembles a network of three B−B σ bonds, the central bond being significantly weaker than the other two.show moreshow less

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Metadaten
Author: Carsten Lenczyk, Dipak Kumar Roy, Kai Oberdorf, Jörn Nitsch, Rian D. Dewhurst, Krzysztof Radacki, Jean-François Halet, Todd B. Marder, Matthias Bickelhaupt, Holger BraunschweigORCiD
URN:urn:nbn:de:bvb:20-opus-214324
Document Type:Journal article
Faculties:Fakultät für Chemie und Pharmazie / Institut für Anorganische Chemie
Language:English
Parent Title (English):Chemistry - A European Journal
Year of Completion:2019
Volume:25
Issue:72
Pagenumber:16544-16549
Source:Chemistry - A European Journal (2019) 25(72):16544-16549. DOI: 10.1002/chem.201904772
DOI:https://doi.org/10.1002/chem.201904772
Dewey Decimal Classification:5 Naturwissenschaften und Mathematik / 54 Chemie / 540 Chemie und zugeordnete Wissenschaften
Tag:B−H activation; boron; dehydrocoupling; ruthenium; transition metal
Release Date:2020/10/22
Licence (German):License LogoCC BY: Creative-Commons-Lizenz: Namensnennung 4.0 International