Iron-Catalyzed H/D Exchange of Primary Silanes, Secondary Silanes and Tertiary Siloxanes

Tom Linford-Wood; Mary Mahon; Matthew Grayson; Ruth Webster

doi:10.1021/acscatal.2c00224

Iron-Catalyzed H/D Exchange of Primary Silanes, Secondary Silanes and Tertiary Siloxanes

Tom Linford-Wood, Mary Mahon, Matthew Grayson, Ruth Webster

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15 Citations (SciVal)

315 Downloads (Pure)

Abstract

A synthetic study into the catalytic hydrogen/deuterium (H/D) exchange of 1° silanes, 2° silanes, and 3° siloxanes is presented, facilitated by iron-β-diketiminato complexes (1a and 1b). Near-complete H/D exchange is observed for a variety of aryl- and alkyl-containing hydrosilanes and hydrosiloxanes. The reaction tolerates alternative hydride source pinacolborane (HBpin), with quantitative H/D exchange. A synthetic and density functional theory (DFT) investigation suggests that a monomeric iron-deuteride is responsible for the H/D exchange.

Original language	English
Pages (from-to)	2979-2985
Number of pages	7
Journal	ACS Catalysis
Volume	12
Issue number	5
Early online date	18 Feb 2022
DOIs	https://doi.org/10.1021/acscatal.2c00224
Publication status	Published - 4 Mar 2022

Bibliographical note

Funding Information:
The EPSRC and the Centre for Doctoral Training in Catalysis (PhD studentship awarded to TGLW) are thanked for funding. Part of this work was completed using the Balena HPC service at the University of Bath ( https://www.bath.ac.uk/corporate-information/balena-hpc-cluster/ ).

Publisher Copyright:
© 2022 American Chemical Society.

Keywords

density functional theory
deuterium labeling
iron catalysis
mechanistic investigations
silanes
siloxanes

ASJC Scopus subject areas

Catalysis
General Chemistry

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10.1021/acscatal.2c00224Licence: CC BY

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Cite this

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AU - Linford-Wood, Tom

AU - Mahon, Mary

AU - Grayson, Matthew

AU - Webster, Ruth

N1 - Funding Information: The EPSRC and the Centre for Doctoral Training in Catalysis (PhD studentship awarded to TGLW) are thanked for funding. Part of this work was completed using the Balena HPC service at the University of Bath ( https://www.bath.ac.uk/corporate-information/balena-hpc-cluster/ ). Publisher Copyright: © 2022 American Chemical Society.

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N2 - A synthetic study into the catalytic hydrogen/deuterium (H/D) exchange of 1° silanes, 2° silanes, and 3° siloxanes is presented, facilitated by iron-β-diketiminato complexes (1a and 1b). Near-complete H/D exchange is observed for a variety of aryl- and alkyl-containing hydrosilanes and hydrosiloxanes. The reaction tolerates alternative hydride source pinacolborane (HBpin), with quantitative H/D exchange. A synthetic and density functional theory (DFT) investigation suggests that a monomeric iron-deuteride is responsible for the H/D exchange.

AB - A synthetic study into the catalytic hydrogen/deuterium (H/D) exchange of 1° silanes, 2° silanes, and 3° siloxanes is presented, facilitated by iron-β-diketiminato complexes (1a and 1b). Near-complete H/D exchange is observed for a variety of aryl- and alkyl-containing hydrosilanes and hydrosiloxanes. The reaction tolerates alternative hydride source pinacolborane (HBpin), with quantitative H/D exchange. A synthetic and density functional theory (DFT) investigation suggests that a monomeric iron-deuteride is responsible for the H/D exchange.

KW - density functional theory

KW - deuterium labeling

KW - iron catalysis

KW - mechanistic investigations

KW - silanes

KW - siloxanes

UR - https://www.scopus.com/pages/publications/85125365909

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DO - 10.1021/acscatal.2c00224

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SN - 2155-5435

VL - 12

SP - 2979

EP - 2985

JO - ACS Catalysis

JF - ACS Catalysis

IS - 5

ER -

Iron-Catalyzed H/D Exchange of Primary Silanes, Secondary Silanes and Tertiary Siloxanes

Abstract

Bibliographical note

Keywords

ASJC Scopus subject areas

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