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

doi:10.1002/chem.201904772

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 Journal › Article › Academic › peer-review

Abstract

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 language	English
Pages (from-to)	16544-16549
Number of pages	6
Journal	Chemistry - A European Journal
Volume	25
Issue number	72
DOIs	https://doi.org/10.1002/chem.201904772
Publication status	Published - 20 Dec 2019

Funding

Financial support from the Deutsche Forschungsgemeinschaft, the Julius-Maximilians-Universität Würzburg and the Netherlands Organisation for Scientific Research (NWO) is gratefully acknowledged. D.K.R. is grateful for a postdoctoral fellowship from the Science and Engineering Research Board (Award no. SB/OS/PDF-052/2016-17) of India.

Funders	Funder number
Deutsche Forschungsgemeinschaft
???publication-publication-funding-organisation-not-added???	16544
Science and Engineering Research Board	SB/OS/PDF-052/2016-17

Keywords

boron
B−H activation
dehydrocoupling
ruthenium
transition metal

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10.1002/chem.201904772

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title = "Toward Transition-Metal-Templated Construction of Arylated B4 Chains by Dihydroborane Dehydrocoupling",

abstract = "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.",

keywords = "boron, B−H activation, dehydrocoupling, ruthenium, transition metal",

author = "Carsten Lenczyk and Roy, \{Dipak Kumar\} and Kai Oberdorf and J{\"o}rn Nitsch and Dewhurst, \{Rian D.\} and Krzysztof Radacki and Halet, \{Jean Fran{\c c}ois\} and Marder, \{Todd B.\} and Matthias Bickelhaupt and Holger Braunschweig",

year = "2019",

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doi = "10.1002/chem.201904772",

language = "English",

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T1 - Toward Transition-Metal-Templated Construction of Arylated B4 Chains by Dihydroborane Dehydrocoupling

AU - Lenczyk, Carsten

AU - Roy, Dipak Kumar

AU - Oberdorf, Kai

AU - Nitsch, Jörn

AU - Dewhurst, Rian D.

AU - Radacki, Krzysztof

AU - Halet, Jean François

AU - Marder, Todd B.

AU - Bickelhaupt, Matthias

AU - Braunschweig, Holger

PY - 2019/12/20

Y1 - 2019/12/20

N2 - 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.

AB - 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.

KW - boron

KW - B−H activation

KW - dehydrocoupling

KW - ruthenium

KW - transition metal

UR - https://www.scopus.com/pages/publications/85076509189

UR - https://www.scopus.com/pages/publications/85076509189#tab=citedBy

U2 - 10.1002/chem.201904772

DO - 10.1002/chem.201904772

M3 - Article

AN - SCOPUS:85076509189

SN - 0947-6539

VL - 25

SP - 16544

EP - 16549

JO - Chemistry - A European Journal

JF - Chemistry - A European Journal

IS - 72

ER -

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

Abstract

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Keywords

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CCDC 1901323: Experimental Crystal Structure Determination

CCDC 1901324: Experimental Crystal Structure Determination

CCDC 1901326: Experimental Crystal Structure Determination

Cite this

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

Abstract

Funding

Keywords

Access to Document

Persistent URL (handle)

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Fingerprint

Datasets

CCDC 1901323: Experimental Crystal Structure Determination

CCDC 1901324: Experimental Crystal Structure Determination

CCDC 1901326: Experimental Crystal Structure Determination

Cite this

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