Geometrically enforced donor-facilitated dehydrocoupling leading to an isolable arsanylidine-phosphorane

Brian Alexander Chalmers; Michael Buehl; Kasun Sankalpa Athukorala Arachchige; Alexandra Martha Zoya Slawin; Petr Kilian

doi:10.1021/ja502625z

Geometrically enforced donor-facilitated dehydrocoupling leading to an isolable arsanylidine-phosphorane

Brian Alexander Chalmers, Michael Buehl, Kasun Sankalpa Athukorala Arachchige, Alexandra Martha Zoya Slawin, Petr Kilian^*

^*Corresponding author for this work

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

39 Citations (Scopus)

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Abstract

A proximate Lewis basic group facilitates the mild dehydrogenative P–As intramolecular coupling in the phosphine-arsine peri-substituted acenaphthene 3, affording thermally and hydrolytically stable arsanylidine-phosphorane 4 with a sterically accessible two-coordinate arsenic atom. The formation of 4 is thermoneutral due to the dehydrogenation being concerted with the donor coordination. Reaction of 4 with a limited amount of oxygen reveals arsinidene-like reactivity via formation of cyclooligoarsines, supporting the formulation of the bonding in 4 as base-stabilized arsinidene R₃P→AsR.

Original language	English
Pages (from-to)	6247-6250
Journal	Journal of the American Chemical Society
Volume	136
Issue number	17
Early online date	15 Apr 2014
DOIs	https://doi.org/10.1021/ja502625z
Publication status	Published - Apr 2014

Keywords

Dehydrocoupling
Arsanylidine-Phosphorane
Cyclooligoarsines
Catenated structures

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10.1021/ja502625zLicence: CC BY

ja502625z
Copyright © 2014 American Chemical Society. This is an open access article available under the terms of the of the Creative Commons Attribution 4.0 International license. Any use of the article is subject to the following conditions: The authors' moral right to the integrity of their work under the Berne Convention (Article 6bis) is not compromised & where content in the article is identified as belonging to a third party, it is your responsibility to ensure that any reuse complies with copyright policies of the owner.
Final published version, 776 KBLicence: CC BY

Structuring the Future: Structuring the Future - Underpinning world-leading science in EaStCHEM through cutting edge characterisation
Woollins, J. D. (PI), Ashbrook, S. E. (CoI), Morris, R. E. (CoI) & Slawin, A. M. Z. (CoI)
EPSRC
1/01/13 → 31/03/13
Project: Standard
Upgrade Small Equipment Base: Small items of research equipment at the University of St Andrews. Supporting a new generation of physical sciences research
Woollins, J. D. (PI)
EPSRC
1/11/12 → 31/03/13
Project: Standard
EP/E010395/1 STABLE PHOSPHORUS CENTRED: Stable Phosphorous Cenred Radicals and Odd Electron Bonds
Kilian, P. (PI)
EPSRC
8/01/07 → 7/01/09
Project: Standard

Petr Kilian
- pk7st-andrews.acuk
- School of Chemistry - Senior Lecturer
- EaSTCHEM
Person: Academic

Cite this

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title = "Geometrically enforced donor-facilitated dehydrocoupling leading to an isolable arsanylidine-phosphorane",

abstract = "A proximate Lewis basic group facilitates the mild dehydrogenative P–As intramolecular coupling in the phosphine-arsine peri-substituted acenaphthene 3, affording thermally and hydrolytically stable arsanylidine-phosphorane 4 with a sterically accessible two-coordinate arsenic atom. The formation of 4 is thermoneutral due to the dehydrogenation being concerted with the donor coordination. Reaction of 4 with a limited amount of oxygen reveals arsinidene-like reactivity via formation of cyclooligoarsines, supporting the formulation of the bonding in 4 as base-stabilized arsinidene R3P→AsR.",

keywords = "Dehydrocoupling, Arsanylidine-Phosphorane, Cyclooligoarsines, Catenated structures ",

author = "Chalmers, {Brian Alexander} and Michael Buehl and {Athukorala Arachchige}, {Kasun Sankalpa} and Slawin, {Alexandra Martha Zoya} and Petr Kilian",

note = "This work was made open access through funds from the RCUK open access block grant.",

year = "2014",

month = apr,

doi = "10.1021/ja502625z",

language = "English",

volume = "136",

pages = "6247--6250",

journal = "Journal of the American Chemical Society",

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T1 - Geometrically enforced donor-facilitated dehydrocoupling leading to an isolable arsanylidine-phosphorane

AU - Chalmers, Brian Alexander

AU - Buehl, Michael

AU - Athukorala Arachchige, Kasun Sankalpa

AU - Slawin, Alexandra Martha Zoya

AU - Kilian, Petr

N1 - This work was made open access through funds from the RCUK open access block grant.

PY - 2014/4

Y1 - 2014/4

N2 - A proximate Lewis basic group facilitates the mild dehydrogenative P–As intramolecular coupling in the phosphine-arsine peri-substituted acenaphthene 3, affording thermally and hydrolytically stable arsanylidine-phosphorane 4 with a sterically accessible two-coordinate arsenic atom. The formation of 4 is thermoneutral due to the dehydrogenation being concerted with the donor coordination. Reaction of 4 with a limited amount of oxygen reveals arsinidene-like reactivity via formation of cyclooligoarsines, supporting the formulation of the bonding in 4 as base-stabilized arsinidene R3P→AsR.

AB - A proximate Lewis basic group facilitates the mild dehydrogenative P–As intramolecular coupling in the phosphine-arsine peri-substituted acenaphthene 3, affording thermally and hydrolytically stable arsanylidine-phosphorane 4 with a sterically accessible two-coordinate arsenic atom. The formation of 4 is thermoneutral due to the dehydrogenation being concerted with the donor coordination. Reaction of 4 with a limited amount of oxygen reveals arsinidene-like reactivity via formation of cyclooligoarsines, supporting the formulation of the bonding in 4 as base-stabilized arsinidene R3P→AsR.

KW - Dehydrocoupling

KW - Arsanylidine-Phosphorane

KW - Cyclooligoarsines

KW - Catenated structures

U2 - 10.1021/ja502625z

DO - 10.1021/ja502625z

M3 - Article

SN - 0002-7863

VL - 136

SP - 6247

EP - 6250

JO - Journal of the American Chemical Society

JF - Journal of the American Chemical Society

IS - 17

ER -

Geometrically enforced donor-facilitated dehydrocoupling leading to an isolable arsanylidine-phosphorane

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Structuring the Future: Structuring the Future - Underpinning world-leading science in EaStCHEM through cutting edge characterisation

Upgrade Small Equipment Base: Small items of research equipment at the University of St Andrews. Supporting a new generation of physical sciences research

EP/E010395/1 STABLE PHOSPHORUS CENTRED: Stable Phosphorous Cenred Radicals and Odd Electron Bonds

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Petr Kilian

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