Stabilization of Diborynes versus Destabilization of Diborenes by Coordination of Lewis Bases: Unravelling the Dichotomy

Lucas de Azevedo Santos; Daniel E. Trujillo-González; J. Oscar C. Jiménez-Halla; F. Matthias Bickelhaupt; Miquel Solà

doi:10.1002/chem.202303185

Stabilization of Diborynes versus Destabilization of Diborenes by Coordination of Lewis Bases: Unravelling the Dichotomy

Lucas de Azevedo Santos
, Daniel E. Trujillo-González
, J. Oscar C. Jiménez-Halla
, F. Matthias Bickelhaupt
, Miquel Solà

Chemical Sciences

Research output: Contribution to journal › Article › peer-review

1 Citation (Scopus)

Abstract

We have quantum chemically investigated the boron-boron bonds in B₂, diborynes B₂L₂, and diborenes B₂H₂L₂ (L=none, OH₂, NH₃) using dispersion-corrected relativistic density functional theory at ZORA-BLYP-D3(BJ)/TZ2P. B₂ has effectively a single B−B bond provided by two half π bonds, whereas B₂H₂ has effectively a double B=B bond provided by two half π bonds and one σ 2p–2p bond. This different electronic structure causes B₂ and B₂H₂ to react differently to the addition of ligands. Thus, in B₂L₂, electron-donating ligands shorten and strengthen the boron-boron bond whereas, in B₂H₂L₂, they lengthen and weaken the boron-boron bond. The aforementioned variations in boron-boron bond length and strength become more pronounced as the Lewis basicity of the ligands L increases.

Original language	English
Article number	e202303185
Journal	Chemistry - A European Journal
Volume	30
Issue number	8
DOIs	https://doi.org/10.1002/chem.202303185
Publication status	Published - 7 Feb 2024

Keywords

Bond theory
Boron
Density functional calculations
Energy decomposition analysis
Multiple boron-boron bonds

ASJC Scopus subject areas

Catalysis
General Chemistry
Organic Chemistry

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10.1002/chem.202303185

Cite this

@article{65a5bea1c0a344a0931514c5765c6736,

title = "Stabilization of Diborynes versus Destabilization of Diborenes by Coordination of Lewis Bases: Unravelling the Dichotomy",

abstract = "We have quantum chemically investigated the boron-boron bonds in B2, diborynes B2L2, and diborenes B2H2L2 (L=none, OH2, NH3) using dispersion-corrected relativistic density functional theory at ZORA-BLYP-D3(BJ)/TZ2P. B2 has effectively a single B−B bond provided by two half π bonds, whereas B2H2 has effectively a double B=B bond provided by two half π bonds and one σ 2p–2p bond. This different electronic structure causes B2 and B2H2 to react differently to the addition of ligands. Thus, in B2L2, electron-donating ligands shorten and strengthen the boron-boron bond whereas, in B2H2L2, they lengthen and weaken the boron-boron bond. The aforementioned variations in boron-boron bond length and strength become more pronounced as the Lewis basicity of the ligands L increases.",

keywords = "Bond theory, Boron, Density functional calculations, Energy decomposition analysis, Multiple boron-boron bonds",

author = "\{de Azevedo Santos\}, Lucas and Trujillo-Gonz{\'a}lez, \{Daniel E.\} and Jim{\'e}nez-Halla, \{J. Oscar C.\} and Bickelhaupt, \{F. Matthias\} and Miquel Sol{\`a}",

note = "Publisher Copyright: {\textcopyright} 2023 The Authors. Chemistry - A European Journal published by Wiley-VCH GmbH.",

year = "2024",

month = feb,

day = "7",

doi = "10.1002/chem.202303185",

language = "English",

volume = "30",

journal = "Chemistry - A European Journal",

issn = "0947-6539",

publisher = "John Wiley and Sons Inc.",

number = "8",

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TY - JOUR

T1 - Stabilization of Diborynes versus Destabilization of Diborenes by Coordination of Lewis Bases

T2 - Unravelling the Dichotomy

AU - de Azevedo Santos, Lucas

AU - Trujillo-González, Daniel E.

AU - Jiménez-Halla, J. Oscar C.

AU - Bickelhaupt, F. Matthias

AU - Solà, Miquel

PY - 2024/2/7

Y1 - 2024/2/7

N2 - We have quantum chemically investigated the boron-boron bonds in B2, diborynes B2L2, and diborenes B2H2L2 (L=none, OH2, NH3) using dispersion-corrected relativistic density functional theory at ZORA-BLYP-D3(BJ)/TZ2P. B2 has effectively a single B−B bond provided by two half π bonds, whereas B2H2 has effectively a double B=B bond provided by two half π bonds and one σ 2p–2p bond. This different electronic structure causes B2 and B2H2 to react differently to the addition of ligands. Thus, in B2L2, electron-donating ligands shorten and strengthen the boron-boron bond whereas, in B2H2L2, they lengthen and weaken the boron-boron bond. The aforementioned variations in boron-boron bond length and strength become more pronounced as the Lewis basicity of the ligands L increases.

AB - We have quantum chemically investigated the boron-boron bonds in B2, diborynes B2L2, and diborenes B2H2L2 (L=none, OH2, NH3) using dispersion-corrected relativistic density functional theory at ZORA-BLYP-D3(BJ)/TZ2P. B2 has effectively a single B−B bond provided by two half π bonds, whereas B2H2 has effectively a double B=B bond provided by two half π bonds and one σ 2p–2p bond. This different electronic structure causes B2 and B2H2 to react differently to the addition of ligands. Thus, in B2L2, electron-donating ligands shorten and strengthen the boron-boron bond whereas, in B2H2L2, they lengthen and weaken the boron-boron bond. The aforementioned variations in boron-boron bond length and strength become more pronounced as the Lewis basicity of the ligands L increases.

KW - Bond theory

KW - Boron

KW - Density functional calculations

KW - Energy decomposition analysis

KW - Multiple boron-boron bonds

UR - https://www.scopus.com/pages/publications/85179727692

U2 - 10.1002/chem.202303185

DO - 10.1002/chem.202303185

M3 - Article

C2 - 37870211

AN - SCOPUS:85179727692

SN - 0947-6539

VL - 30

JO - Chemistry - A European Journal

JF - Chemistry - A European Journal

IS - 8

M1 - e202303185

ER -

Stabilization of Diborynes versus Destabilization of Diborenes by Coordination of Lewis Bases: Unravelling the Dichotomy

Abstract

Keywords

ASJC Scopus subject areas

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University of Guanajuato Reports Findings in Science (Stabilization of Diborynes versus Destabilization of Diborenes by Coordination of Lewis Bases. Unraveling the Dichotomy)

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Stabilization of Diborynes versus Destabilization of Diborenes by Coordination of Lewis Bases: Unravelling the Dichotomy

Abstract

Keywords

ASJC Scopus subject areas

Access to Document

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University of Guanajuato Reports Findings in Science (Stabilization of Diborynes versus Destabilization of Diborenes by Coordination of Lewis Bases. Unraveling the Dichotomy)

Cite this