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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.…
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 |
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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): | CC BY: Creative-Commons-Lizenz: Namensnennung 4.0 International |