A Terphenyl Supported Dioxophosphorane Dimer: the Light Congener of Lawesson's and Woollins’ Reagents

Laura E. English; Aleksandra Pajak; Claire L. McMullin; John P. Lowe; Mary F. Mahon; David J. Liptrot

doi:10.1002/chem.202200376

A Terphenyl Supported Dioxophosphorane Dimer: the Light Congener of Lawesson's and Woollins’ Reagents

Laura E. English, Aleksandra Pajak, Claire L. McMullin, John P. Lowe, Mary F. Mahon, David J. Liptrot

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

1 Citation (SciVal)

Abstract

Thermolysis of a 1,3-dioxa-2-phospholane supported by the terphenyl ligand Ar^iPr4 (Ar^iPr4=[C₆H₃-2,6-(C₆H₃-2,6-iPr₂)]) at 150 °C gives [Ar^iPr4PO₂]₂ via loss of ethene. [Ar^iPr4PO₂]₂ was characterised by X-ray crystallography and NMR spectroscopy; it contains a 4-membered P−O−P−O ring and is the isostructural oxygen analogue of Lawesson's and Woollins’ reagents. The dimeric structure of [Ar^iPr4PO₂]₂ was found to persist in solution through VT NMR spectroscopy and DOSY, supported by DFT calculations. The addition of DMAP to the 1,3-dioxa-2-phospholane facilitates the loss of ethene to give Ar^iPr4(DMAP)PO₂ after days at room temperature, with this product also characterised by X-ray crystallography and NMR spectroscopy. Replacement of the DMAP with pyridine induces ethene loss from the 1,3-dioxa-2-phospholane to provide gram-scale samples of [Ar^iPr4PO₂]₂ in 75 % yield in 2 days at only 100 °C.

Original language	English
Article number	e202200376
Journal	Chemistry - A European Journal
Volume	28
Issue number	28
Early online date	6 Apr 2022
DOIs	https://doi.org/10.1002/chem.202200376
Publication status	Published - 16 May 2022

Bibliographical note

Funding Information:
DJL thanks the Royal Society for the support of a University Research Fellowship. We wish to thank the EPSRC for funding, MC for use of their analysis facilities, and the Anatra High Throughput Computing (HTC) Cluster at the University of Bath. We would like to thank the EPSRC for funding (EP/L016354/1) for a PhD studentship for LEE. 2

Keywords

arene ligands
chalcogens
organocatalysis
phosphorus heterocycles

ASJC Scopus subject areas

Catalysis
Organic Chemistry

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10.1002/chem.202200376Licence: CC BY

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title = "A Terphenyl Supported Dioxophosphorane Dimer: the Light Congener of Lawesson's and Woollins{\textquoteright} Reagents",

abstract = "Thermolysis of a 1,3-dioxa-2-phospholane supported by the terphenyl ligand AriPr4 (AriPr4=[C6H3-2,6-(C6H3-2,6-iPr2)]) at 150 °C gives [AriPr4PO2]2 via loss of ethene. [AriPr4PO2]2 was characterised by X-ray crystallography and NMR spectroscopy; it contains a 4-membered P−O−P−O ring and is the isostructural oxygen analogue of Lawesson's and Woollins{\textquoteright} reagents. The dimeric structure of [AriPr4PO2]2 was found to persist in solution through VT NMR spectroscopy and DOSY, supported by DFT calculations. The addition of DMAP to the 1,3-dioxa-2-phospholane facilitates the loss of ethene to give AriPr4(DMAP)PO2 after days at room temperature, with this product also characterised by X-ray crystallography and NMR spectroscopy. Replacement of the DMAP with pyridine induces ethene loss from the 1,3-dioxa-2-phospholane to provide gram-scale samples of [AriPr4PO2]2 in 75 % yield in 2 days at only 100 °C.",

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note = "Funding Information: DJL thanks the Royal Society for the support of a University Research Fellowship. We wish to thank the EPSRC for funding, MC for use of their analysis facilities, and the Anatra High Throughput Computing (HTC) Cluster at the University of Bath. We would like to thank the EPSRC for funding (EP/L016354/1) for a PhD studentship for LEE. 2 ",

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AU - McMullin, Claire L.

AU - Lowe, John P.

AU - Mahon, Mary F.

AU - Liptrot, David J.

N1 - Funding Information: DJL thanks the Royal Society for the support of a University Research Fellowship. We wish to thank the EPSRC for funding, MC for use of their analysis facilities, and the Anatra High Throughput Computing (HTC) Cluster at the University of Bath. We would like to thank the EPSRC for funding (EP/L016354/1) for a PhD studentship for LEE. 2

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N2 - Thermolysis of a 1,3-dioxa-2-phospholane supported by the terphenyl ligand AriPr4 (AriPr4=[C6H3-2,6-(C6H3-2,6-iPr2)]) at 150 °C gives [AriPr4PO2]2 via loss of ethene. [AriPr4PO2]2 was characterised by X-ray crystallography and NMR spectroscopy; it contains a 4-membered P−O−P−O ring and is the isostructural oxygen analogue of Lawesson's and Woollins’ reagents. The dimeric structure of [AriPr4PO2]2 was found to persist in solution through VT NMR spectroscopy and DOSY, supported by DFT calculations. The addition of DMAP to the 1,3-dioxa-2-phospholane facilitates the loss of ethene to give AriPr4(DMAP)PO2 after days at room temperature, with this product also characterised by X-ray crystallography and NMR spectroscopy. Replacement of the DMAP with pyridine induces ethene loss from the 1,3-dioxa-2-phospholane to provide gram-scale samples of [AriPr4PO2]2 in 75 % yield in 2 days at only 100 °C.

AB - Thermolysis of a 1,3-dioxa-2-phospholane supported by the terphenyl ligand AriPr4 (AriPr4=[C6H3-2,6-(C6H3-2,6-iPr2)]) at 150 °C gives [AriPr4PO2]2 via loss of ethene. [AriPr4PO2]2 was characterised by X-ray crystallography and NMR spectroscopy; it contains a 4-membered P−O−P−O ring and is the isostructural oxygen analogue of Lawesson's and Woollins’ reagents. The dimeric structure of [AriPr4PO2]2 was found to persist in solution through VT NMR spectroscopy and DOSY, supported by DFT calculations. The addition of DMAP to the 1,3-dioxa-2-phospholane facilitates the loss of ethene to give AriPr4(DMAP)PO2 after days at room temperature, with this product also characterised by X-ray crystallography and NMR spectroscopy. Replacement of the DMAP with pyridine induces ethene loss from the 1,3-dioxa-2-phospholane to provide gram-scale samples of [AriPr4PO2]2 in 75 % yield in 2 days at only 100 °C.

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A Terphenyl Supported Dioxophosphorane Dimer: the Light Congener of Lawesson's and Woollins’ Reagents

Abstract

Bibliographical note

Keywords

ASJC Scopus subject areas

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Cite this

A Terphenyl Supported Dioxophosphorane Dimer: the Light Congener of Lawesson's and Woollins’ Reagents

Abstract

Bibliographical note

Keywords

ASJC Scopus subject areas

Access to Document

Other files and links

Fingerprint

Equipment

High Performance Computing (HPC) Facility

Cite this