Bridges and vertices in heteroboranes

Stuart A. Macgregor; Alan J. Welch

doi:10.3390/molecules28010190

Bridges and vertices in heteroboranes

Stuart A. Macgregor^*, Alan J. Welch^*

^*Corresponding author for this work

School of Chemistry

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

Abstract

A number of (hetero)boranes are known in which a main group atom X ‘bridges’ a B—B connectivity in the open face, and in such species X has previously been described as simply a bridge or, alternatively, as a vertex in a larger cluster. In this study we describe an approach to distinguish between these options based on identifying the best fit of the experimental {B_x} cluster fragment with alternate exemplar {B_x} fragments derived from DFT-optimized [B_nH_n]²⁻ models. In most of the examples studied atom X is found to be better regarded as a vertex, having ‘a ‘verticity’ of ca. 60–65%. Consideration of our results leads to the suggestion that the radial electron contribution from X to the overall skeletal electron count is more significant than the tangential contribution.

Original language	English
Article number	190
Number of pages	17
Journal	Molecules
Volume	28
Issue number	1
DOIs	https://doi.org/10.3390/molecules28010190
Publication status	Published - 26 Dec 2022

Keywords

Boron cluster
Heteroborane
Bridge
Vertex
Structure
Crystal structure
DFT calculation

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Macgregor_2022_Molecules_Bridges-and-vertices-in-heteroboranes_CC
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Cite this

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title = "Bridges and vertices in heteroboranes",

abstract = "A number of (hetero)boranes are known in which a main group atom X {\textquoteleft}bridges{\textquoteright} a B—B connectivity in the open face, and in such species X has previously been described as simply a bridge or, alternatively, as a vertex in a larger cluster. In this study we describe an approach to distinguish between these options based on identifying the best fit of the experimental {Bx} cluster fragment with alternate exemplar {Bx} fragments derived from DFT-optimized [BnHn]2− models. In most of the examples studied atom X is found to be better regarded as a vertex, having {\textquoteleft}a {\textquoteleft}verticity{\textquoteright} of ca. 60–65%. Consideration of our results leads to the suggestion that the radial electron contribution from X to the overall skeletal electron count is more significant than the tangential contribution.",

keywords = "Boron cluster, Heteroborane, Bridge, Vertex, Structure, Crystal structure, DFT calculation",

author = "Macgregor, {Stuart A.} and Welch, {Alan J.}",

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doi = "10.3390/molecules28010190",

language = "English",

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TY - JOUR

T1 - Bridges and vertices in heteroboranes

AU - Macgregor, Stuart A.

AU - Welch, Alan J.

PY - 2022/12/26

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N2 - A number of (hetero)boranes are known in which a main group atom X ‘bridges’ a B—B connectivity in the open face, and in such species X has previously been described as simply a bridge or, alternatively, as a vertex in a larger cluster. In this study we describe an approach to distinguish between these options based on identifying the best fit of the experimental {Bx} cluster fragment with alternate exemplar {Bx} fragments derived from DFT-optimized [BnHn]2− models. In most of the examples studied atom X is found to be better regarded as a vertex, having ‘a ‘verticity’ of ca. 60–65%. Consideration of our results leads to the suggestion that the radial electron contribution from X to the overall skeletal electron count is more significant than the tangential contribution.

AB - A number of (hetero)boranes are known in which a main group atom X ‘bridges’ a B—B connectivity in the open face, and in such species X has previously been described as simply a bridge or, alternatively, as a vertex in a larger cluster. In this study we describe an approach to distinguish between these options based on identifying the best fit of the experimental {Bx} cluster fragment with alternate exemplar {Bx} fragments derived from DFT-optimized [BnHn]2− models. In most of the examples studied atom X is found to be better regarded as a vertex, having ‘a ‘verticity’ of ca. 60–65%. Consideration of our results leads to the suggestion that the radial electron contribution from X to the overall skeletal electron count is more significant than the tangential contribution.

KW - Boron cluster

KW - Heteroborane

KW - Bridge

KW - Vertex

KW - Structure

KW - Crystal structure

KW - DFT calculation

U2 - 10.3390/molecules28010190

DO - 10.3390/molecules28010190

M3 - Article

C2 - 36615384

SN - 1420-3049

VL - 28

JO - Molecules

JF - Molecules

IS - 1

M1 - 190

ER -

Bridges and vertices in heteroboranes

Abstract

Keywords

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