Hydride abstraction and deprotonation – an efficient route to low co-ordinate phosphorus and arsenic species

Laurence John Taylor; Michael Buehl; Piotr Wawrzyniak; Brian Alexander Chalmers; J Derek Woollins; Alexandra Martha Zoya Slawin; Amy Fuller; Petr Kilian

doi:10.1002/ejic.201500948

Hydride abstraction and deprotonation – an efficient route to low co-ordinate phosphorus and arsenic species

Laurence John Taylor, Michael Buehl, Piotr Wawrzyniak, Brian Alexander Chalmers, J Derek Woollins, Alexandra Martha Zoya Slawin, Amy Fuller, Petr Kilian

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

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Abstract

Treatment of Acenap(PiPr₂)(EH₂) (Acenap = acenaphthene-5,6-diyl; 1a, E = As; 1b, E = P) with Ph₃C·BF₄ resulted in hydride abstraction to give [Acenap(PiPr₂)(EH)][BF₄] (2a, E = As; 2b, E = P). These represent the first structurally characterised phosphino/arsino-phosphonium salts with secondary arsine/phosphine groups, as well as the first example of a Lewis base stabilised primary arsenium cation. Compounds 2a and 2b were deprotonated with NaH to afford low co-ordinate species Acenap(PiPr₂)(E) (3a, E = As; 3b, E = P). This provides an alternative and practical synthetic pathway to the phosphanylidene-σ4-phosphorane 3b and provides mechanistic insight into the formation of arsanylidene-σ4-phosphorane 3a, indirectly supporting the hypothesis that the previously reported dehydrogenation of 1a occurs via an ionic mechanism.

Original language	English
Journal	European Journal of Inorganic Chemistry
Volume	Early view
Early online date	6 Oct 2015
DOIs	https://doi.org/10.1002/ejic.201500948
Publication status	Published - 2015

Keywords

Phosphorus
Arsenic
Low co-ordinate
Peri-substitution
Base-stabilisation

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10.1002/ejic.201500948

Woollins_2015_EJIC_Hydride_AM
Copyright © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim. This work is made available online in accordance with the publisher’s policies. This is the author created, accepted version manuscript following peer review and may differ slightly from the final published version. The final published version of this work is available at https://dx.doi.org/10.1002/ejic.201500948
Accepted author manuscript, 1.28 MB
Woollins_2015_EJIC_Hydride_Supplement_AM
Copyright © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim. This work is made available online in accordance with the publisher’s policies. This is the author created, accepted version manuscript following peer review and may differ slightly from the final published version. The final published version of this work is available at https://dx.doi.org/10.1002/ejic.201500948
Accepted author manuscript, 660 KB

Cite this

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title = "Hydride abstraction and deprotonation – an efficient route to low co-ordinate phosphorus and arsenic species",

abstract = "Treatment of Acenap(PiPr2)(EH2) (Acenap = acenaphthene-5,6-diyl; 1a, E = As; 1b, E = P) with Ph3C·BF4 resulted in hydride abstraction to give [Acenap(PiPr2)(EH)][BF4] (2a, E = As; 2b, E = P). These represent the first structurally characterised phosphino/arsino-phosphonium salts with secondary arsine/phosphine groups, as well as the first example of a Lewis base stabilised primary arsenium cation. Compounds 2a and 2b were deprotonated with NaH to afford low co-ordinate species Acenap(PiPr2)(E) (3a, E = As; 3b, E = P). This provides an alternative and practical synthetic pathway to the phosphanylidene-σ4-phosphorane 3b and provides mechanistic insight into the formation of arsanylidene-σ4-phosphorane 3a, indirectly supporting the hypothesis that the previously reported dehydrogenation of 1a occurs via an ionic mechanism.",

keywords = "Phosphorus, Arsenic, Low co-ordinate, Peri-substitution, Base-stabilisation",

author = "Taylor, {Laurence John} and Michael Buehl and Piotr Wawrzyniak and Chalmers, {Brian Alexander} and Woollins, {J Derek} and Slawin, {Alexandra Martha Zoya} and Amy Fuller and Petr Kilian",

note = "This work was financially supported by the EPSRC and COST action grant CM1302 (SIPs). ",

year = "2015",

doi = "10.1002/ejic.201500948",

language = "English",

volume = "Early view",

journal = "European Journal of Inorganic Chemistry",

issn = "1434-1948",

publisher = "Wiley-Blackwell",

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TY - JOUR

T1 - Hydride abstraction and deprotonation – an efficient route to low co-ordinate phosphorus and arsenic species

AU - Taylor, Laurence John

AU - Buehl, Michael

AU - Wawrzyniak, Piotr

AU - Chalmers, Brian Alexander

AU - Woollins, J Derek

AU - Slawin, Alexandra Martha Zoya

AU - Fuller, Amy

AU - Kilian, Petr

N1 - This work was financially supported by the EPSRC and COST action grant CM1302 (SIPs).

PY - 2015

Y1 - 2015

N2 - Treatment of Acenap(PiPr2)(EH2) (Acenap = acenaphthene-5,6-diyl; 1a, E = As; 1b, E = P) with Ph3C·BF4 resulted in hydride abstraction to give [Acenap(PiPr2)(EH)][BF4] (2a, E = As; 2b, E = P). These represent the first structurally characterised phosphino/arsino-phosphonium salts with secondary arsine/phosphine groups, as well as the first example of a Lewis base stabilised primary arsenium cation. Compounds 2a and 2b were deprotonated with NaH to afford low co-ordinate species Acenap(PiPr2)(E) (3a, E = As; 3b, E = P). This provides an alternative and practical synthetic pathway to the phosphanylidene-σ4-phosphorane 3b and provides mechanistic insight into the formation of arsanylidene-σ4-phosphorane 3a, indirectly supporting the hypothesis that the previously reported dehydrogenation of 1a occurs via an ionic mechanism.

AB - Treatment of Acenap(PiPr2)(EH2) (Acenap = acenaphthene-5,6-diyl; 1a, E = As; 1b, E = P) with Ph3C·BF4 resulted in hydride abstraction to give [Acenap(PiPr2)(EH)][BF4] (2a, E = As; 2b, E = P). These represent the first structurally characterised phosphino/arsino-phosphonium salts with secondary arsine/phosphine groups, as well as the first example of a Lewis base stabilised primary arsenium cation. Compounds 2a and 2b were deprotonated with NaH to afford low co-ordinate species Acenap(PiPr2)(E) (3a, E = As; 3b, E = P). This provides an alternative and practical synthetic pathway to the phosphanylidene-σ4-phosphorane 3b and provides mechanistic insight into the formation of arsanylidene-σ4-phosphorane 3a, indirectly supporting the hypothesis that the previously reported dehydrogenation of 1a occurs via an ionic mechanism.

KW - Phosphorus

KW - Arsenic

KW - Low co-ordinate

KW - Peri-substitution

KW - Base-stabilisation

UR - http://onlinelibrary.wiley.com/doi/10.1002/ejic.201500948/suppinfo

U2 - 10.1002/ejic.201500948

DO - 10.1002/ejic.201500948

M3 - Article

SN - 1434-1948

VL - Early view

JO - European Journal of Inorganic Chemistry

JF - European Journal of Inorganic Chemistry

ER -

Hydride abstraction and deprotonation – an efficient route to low co-ordinate phosphorus and arsenic species

Abstract

Keywords

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