The Complex Reactivity of [(salen)Fe]2(μ-O) with HBpin and its Implications in Catalysis

Thomas M. Hood; Samantha Lau; Martin Diefenbach; Leah Firmstone; Mary Mahon; Vera Krewald; Ruth L. Webster

doi:10.1021/acscatal.3c02898

The Complex Reactivity of [(salen)Fe]₂(μ-O) with HBpin and its Implications in Catalysis

Thomas M. Hood, Samantha Lau, Martin Diefenbach, Leah Firmstone, Mary Mahon, Vera Krewald, Ruth L. Webster

Department of Chemistry

Technische Universität Darmstadt

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

2 Citations (SciVal)

Abstract

We report a detailed study into the method of precatalyst activation during alkyne cyclotrimerization. During these studies we have prepared a homologous series of Fe(III)-μ-oxo(salen) complexes and use a range of techniques including UV–vis, reaction monitoring studies, single crystal X-ray diffraction, NMR spectroscopy, and LIFDI mass spectrometry to provide experimental evidence for the nature of the on-cycle iron catalyst. These data infer the likelihood of ligand reduction, generating an iron(salan)-boryl complex as a key on-cycle intermediate. We use DFT studies to interrogate spin states, connecting this to experimentally identified diamagnetic and paramagnetic species. The extreme conformational flexibility of the salan system appears connected to challenges associated with crystallization of likely on-cycle species.

Original language	English
Pages (from-to)	11841 - 11850
Number of pages	10
Journal	ACS Catalysis
Volume	13
Issue number	17
Early online date	23 Aug 2023
DOIs	https://doi.org/10.1021/acscatal.3c02898
Publication status	Published - 1 Sept 2023

Bibliographical note

Funding Information:
The EPSRC (R.L.W., S.L.) and Leverhulme Trust (TMH, MD) are thanked for funding. L.F. thanks the Royal Society of Chemistry for provision of an undergraduate summer studentship. We gratefully acknowledge Professor Ian Fairlamb and Karl Heaton (University of York) for instrument time and assistance with LIFDI-MS measurements. Calculations for this research were conducted on the Lichtenberg high performance computer of the TU Darmstadt.

Keywords

cyclotrimerization
iron
ligand reduction
mechanism
salen

ASJC Scopus subject areas

General Chemistry
Catalysis

Access to Document

10.1021/acscatal.3c02898Licence: CC BY

Cite this

@article{622efb5b03dd4ea4a13fab370da5f0b6,

title = "The Complex Reactivity of [(salen)Fe]2(μ-O) with HBpin and its Implications in Catalysis",

abstract = "We report a detailed study into the method of precatalyst activation during alkyne cyclotrimerization. During these studies we have prepared a homologous series of Fe(III)-μ-oxo(salen) complexes and use a range of techniques including UV–vis, reaction monitoring studies, single crystal X-ray diffraction, NMR spectroscopy, and LIFDI mass spectrometry to provide experimental evidence for the nature of the on-cycle iron catalyst. These data infer the likelihood of ligand reduction, generating an iron(salan)-boryl complex as a key on-cycle intermediate. We use DFT studies to interrogate spin states, connecting this to experimentally identified diamagnetic and paramagnetic species. The extreme conformational flexibility of the salan system appears connected to challenges associated with crystallization of likely on-cycle species.",

keywords = "cyclotrimerization, iron, ligand reduction, mechanism, salen",

author = "Hood, {Thomas M.} and Samantha Lau and Martin Diefenbach and Leah Firmstone and Mary Mahon and Vera Krewald and Webster, {Ruth L.}",

note = "Funding Information: The EPSRC (R.L.W., S.L.) and Leverhulme Trust (TMH, MD) are thanked for funding. L.F. thanks the Royal Society of Chemistry for provision of an undergraduate summer studentship. We gratefully acknowledge Professor Ian Fairlamb and Karl Heaton (University of York) for instrument time and assistance with LIFDI-MS measurements. Calculations for this research were conducted on the Lichtenberg high performance computer of the TU Darmstadt. ",

year = "2023",

month = sep,

day = "1",

doi = "10.1021/acscatal.3c02898",

language = "English",

volume = "13",

pages = "11841 -- 11850",

journal = "ACS Catalysis",

issn = "2155-5435",

publisher = "American Chemical Society",

number = "17",

}

TY - JOUR

T1 - The Complex Reactivity of [(salen)Fe]2(μ-O) with HBpin and its Implications in Catalysis

AU - Hood, Thomas M.

AU - Lau, Samantha

AU - Diefenbach, Martin

AU - Firmstone, Leah

AU - Mahon, Mary

AU - Krewald, Vera

AU - Webster, Ruth L.

N1 - Funding Information: The EPSRC (R.L.W., S.L.) and Leverhulme Trust (TMH, MD) are thanked for funding. L.F. thanks the Royal Society of Chemistry for provision of an undergraduate summer studentship. We gratefully acknowledge Professor Ian Fairlamb and Karl Heaton (University of York) for instrument time and assistance with LIFDI-MS measurements. Calculations for this research were conducted on the Lichtenberg high performance computer of the TU Darmstadt.

PY - 2023/9/1

Y1 - 2023/9/1

N2 - We report a detailed study into the method of precatalyst activation during alkyne cyclotrimerization. During these studies we have prepared a homologous series of Fe(III)-μ-oxo(salen) complexes and use a range of techniques including UV–vis, reaction monitoring studies, single crystal X-ray diffraction, NMR spectroscopy, and LIFDI mass spectrometry to provide experimental evidence for the nature of the on-cycle iron catalyst. These data infer the likelihood of ligand reduction, generating an iron(salan)-boryl complex as a key on-cycle intermediate. We use DFT studies to interrogate spin states, connecting this to experimentally identified diamagnetic and paramagnetic species. The extreme conformational flexibility of the salan system appears connected to challenges associated with crystallization of likely on-cycle species.

AB - We report a detailed study into the method of precatalyst activation during alkyne cyclotrimerization. During these studies we have prepared a homologous series of Fe(III)-μ-oxo(salen) complexes and use a range of techniques including UV–vis, reaction monitoring studies, single crystal X-ray diffraction, NMR spectroscopy, and LIFDI mass spectrometry to provide experimental evidence for the nature of the on-cycle iron catalyst. These data infer the likelihood of ligand reduction, generating an iron(salan)-boryl complex as a key on-cycle intermediate. We use DFT studies to interrogate spin states, connecting this to experimentally identified diamagnetic and paramagnetic species. The extreme conformational flexibility of the salan system appears connected to challenges associated with crystallization of likely on-cycle species.

KW - cyclotrimerization

KW - iron

KW - ligand reduction

KW - mechanism

KW - salen

UR - http://www.scopus.com/inward/record.url?scp=85170040820&partnerID=8YFLogxK

U2 - 10.1021/acscatal.3c02898

DO - 10.1021/acscatal.3c02898

M3 - Article

SN - 2155-5435

VL - 13

SP - 11841

EP - 11850

JO - ACS Catalysis

JF - ACS Catalysis

IS - 17

ER -