Steric Effects Dictate the Formation of Terminal Arylborylene Complexes of Ruthenium from Dihydroboranes

Carsten Lenczyk; Dipak Kumar Roy; Jörn Nitsch; Krzysztof Radacki; Florian Rauch; Rian D. Dewhurst; F. Matthias Bickelhaupt; Todd B. Marder; Holger Braunschweig

doi:10.1002/chem.201902890

Steric Effects Dictate the Formation of Terminal Arylborylene Complexes of Ruthenium from Dihydroboranes

Carsten Lenczyk, Dipak Kumar Roy, Jörn Nitsch, Krzysztof Radacki, Florian Rauch, Rian D. Dewhurst, F. Matthias Bickelhaupt, Todd B. Marder, Holger Braunschweig^*

^*Corresponding author for this work

Research output: Contribution to Journal › Article › Academic › peer-review

Abstract

The steric and electronic properties of aryl substituents in monoaryl borohydrides (Li[ArBH₃]) and dihydroboranes were systematically varied and their reactions with [Ru(PCy₃)₂HCl(H₂)] (Cy: cyclohexyl) were studied, resulting in bis(σ)-borane or terminal borylene complexes of ruthenium. These variations allowed for the investigation of the factors involved in the activation of dihydroboranes in the synthesis of terminal borylene complexes. The complexes were studied by multinuclear NMR spectroscopy, mass spectrometry, X-ray diffraction analysis, and density functional theory (DFT) calculations. The experimental and computational results suggest that the ortho-substitution of the aryl groups is necessary for the formation of terminal borylene complexes.

Original language	English
Pages (from-to)	13566-13571
Number of pages	6
Journal	Chemistry - A European Journal
Volume	25
Issue number	59
Early online date	21 Aug 2019
DOIs	https://doi.org/10.1002/chem.201902890
Publication status	Published - 22 Oct 2019

Keywords

boranes
borohydrides
borylenes
sigma boranes
steric effects

UN SDGs

This output contributes to the following UN Sustainable Development Goals (SDGs)

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10.1002/chem.201902890

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@article{72d88d39560b4f4fb903778d506cf4e5,

title = "Steric Effects Dictate the Formation of Terminal Arylborylene Complexes of Ruthenium from Dihydroboranes",

abstract = "The steric and electronic properties of aryl substituents in monoaryl borohydrides (Li[ArBH3]) and dihydroboranes were systematically varied and their reactions with [Ru(PCy3)2HCl(H2)] (Cy: cyclohexyl) were studied, resulting in bis(σ)-borane or terminal borylene complexes of ruthenium. These variations allowed for the investigation of the factors involved in the activation of dihydroboranes in the synthesis of terminal borylene complexes. The complexes were studied by multinuclear NMR spectroscopy, mass spectrometry, X-ray diffraction analysis, and density functional theory (DFT) calculations. The experimental and computational results suggest that the ortho-substitution of the aryl groups is necessary for the formation of terminal borylene complexes.",

keywords = "boranes, borohydrides, borylenes, sigma boranes, steric effects",

author = "Carsten Lenczyk and Roy, {Dipak Kumar} and J{\"o}rn Nitsch and Krzysztof Radacki and Florian Rauch and Dewhurst, {Rian D.} and Bickelhaupt, {F. Matthias} and Marder, {Todd B.} and Holger Braunschweig",

year = "2019",

month = oct,

day = "22",

doi = "10.1002/chem.201902890",

language = "English",

volume = "25",

pages = "13566--13571",

journal = "Chemistry: A European Journal",

issn = "0947-6539",

publisher = "Wiley-VCH Verlag",

number = "59",

}

TY - JOUR

T1 - Steric Effects Dictate the Formation of Terminal Arylborylene Complexes of Ruthenium from Dihydroboranes

AU - Lenczyk, Carsten

AU - Roy, Dipak Kumar

AU - Nitsch, Jörn

AU - Radacki, Krzysztof

AU - Rauch, Florian

AU - Dewhurst, Rian D.

AU - Bickelhaupt, F. Matthias

AU - Marder, Todd B.

AU - Braunschweig, Holger

PY - 2019/10/22

Y1 - 2019/10/22

N2 - The steric and electronic properties of aryl substituents in monoaryl borohydrides (Li[ArBH3]) and dihydroboranes were systematically varied and their reactions with [Ru(PCy3)2HCl(H2)] (Cy: cyclohexyl) were studied, resulting in bis(σ)-borane or terminal borylene complexes of ruthenium. These variations allowed for the investigation of the factors involved in the activation of dihydroboranes in the synthesis of terminal borylene complexes. The complexes were studied by multinuclear NMR spectroscopy, mass spectrometry, X-ray diffraction analysis, and density functional theory (DFT) calculations. The experimental and computational results suggest that the ortho-substitution of the aryl groups is necessary for the formation of terminal borylene complexes.

AB - The steric and electronic properties of aryl substituents in monoaryl borohydrides (Li[ArBH3]) and dihydroboranes were systematically varied and their reactions with [Ru(PCy3)2HCl(H2)] (Cy: cyclohexyl) were studied, resulting in bis(σ)-borane or terminal borylene complexes of ruthenium. These variations allowed for the investigation of the factors involved in the activation of dihydroboranes in the synthesis of terminal borylene complexes. The complexes were studied by multinuclear NMR spectroscopy, mass spectrometry, X-ray diffraction analysis, and density functional theory (DFT) calculations. The experimental and computational results suggest that the ortho-substitution of the aryl groups is necessary for the formation of terminal borylene complexes.

KW - boranes

KW - borohydrides

KW - borylenes

KW - sigma boranes

KW - steric effects

UR - http://www.scopus.com/inward/record.url?scp=85073668474&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=85073668474&partnerID=8YFLogxK

U2 - 10.1002/chem.201902890

DO - 10.1002/chem.201902890

M3 - Article

C2 - 31433081

AN - SCOPUS:85073668474

VL - 25

SP - 13566

EP - 13571

JO - Chemistry: A European Journal

JF - Chemistry: A European Journal

SN - 0947-6539

IS - 59

ER -

Steric Effects Dictate the Formation of Terminal Arylborylene Complexes of Ruthenium from Dihydroboranes

Abstract

Keywords

UN SDGs

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CCDC 1922480: Experimental Crystal Structure Determination

CCDC 1922482: Experimental Crystal Structure Determination

CCDC 1922473: Experimental Crystal Structure Determination

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Steric Effects Dictate the Formation of Terminal Arylborylene Complexes of Ruthenium from Dihydroboranes

Abstract

Keywords

UN SDGs

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Datasets

CCDC 1922480: Experimental Crystal Structure Determination

CCDC 1922482: Experimental Crystal Structure Determination

CCDC 1922473: Experimental Crystal Structure Determination

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