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

Autor: Krzysztof Radacki, Todd B. Marder, Jörn Nitsch, Carsten Lenczyk, Dipak Kumar Roy, Kai Oberdorf, Rian D. Dewhurst, F. Matthias Bickelhaupt, Holger Braunschweig, Jean-François Halet
Přispěvatelé: Julius-Maximilians-Universität Würzburg [Wurtzbourg, Allemagne] (JMU), Indian Institute of Technology Indore (IITI), Institut des Sciences Chimiques de Rennes (ISCR), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA), Department of Theoretical Chemistry and Amsterdam Centre for Multiscale Modeling (ACMM) VU University Amsterdam (ACMM), VU University Amsterdam, Vrije Universiteit Amsterdam [Amsterdam] (VU), Radboud university [Nijmegen], Deutsche ForschungsgemeinschaftGerman Research Foundation (DFG), Julius-Maximilians-Universitat Wurzburg, Netherlands Organisation for Scientific Research (NWO)Netherlands Organization for Scientific Research (NWO), Science and Engineering Research Board of India [SB/OS/PDF-052/2016-17], Chemistry and Pharmaceutical Sciences, AIMMS, Vrije universiteit = Free university of Amsterdam [Amsterdam] (VU), Julius-Maximilians-Universität Würzburg (JMU), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Radboud University [Nijmegen]
Rok vydání: 2019
Předmět:
Zdroj: Chemistry-A European Journal
Chemistry-A European Journal, Wiley-VCH Verlag, 2019, 25 (72), pp.16544-16549. ⟨10.1002/chem.201904772⟩
Lenczyk, C, Roy, D K, Oberdorf, K, Nitsch, J, Dewhurst, R D, Radacki, K, Halet, J F, Marder, T B, Bickelhaupt, M & Braunschweig, H 2019, ' Toward Transition-Metal-Templated Construction of Arylated B 4 Chains by Dihydroborane Dehydrocoupling ', Chemistry-A European Journal, vol. 25, no. 72, pp. 16544-16549 . https://doi.org/10.1002/chem.201904772
Chemistry-A European Journal, 25(72), 16544-16549. Wiley-VCH Verlag
Chemistry : a European Journal, 25, 72, pp. 16544-16549
Chemistry : a European Journal, 25, 16544-16549
Chemistry-A European Journal, 2019, 25 (72), pp.16544-16549. ⟨10.1002/chem.201904772⟩
ISSN: 0947-6539
1521-3765
DOI: 10.1002/chem.201904772
Popis: 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.
Databáze: OpenAIRE
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