Synthetic and structural study of peri-substituted phosphine-arsines

Brian A. Chalmers; Upulani Somisara; Brian Andrew  Surgenor; Kasun S. Athukorala Arachchige; J Derek Woollins; Michael Buehl; Alexandra M. Z. Slawin; Petr Kilian

doi:10.3390/molecules26237222

Synthetic and structural study of peri-substituted phosphine-arsines

Brian A. Chalmers, Upulani Somisara, Brian Andrew Surgenor, Kasun S. Athukorala Arachchige, J Derek Woollins, Michael Buehl, Alexandra M. Z. Slawin, Petr Kilian

School of Chemistry

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

Abstract

A series of phosphorus-arsenic peri-substituted acenaphthene species have been isolated and fully characterised, including single crystal X-ray diffraction. Reactions of EBr₃ (E = P, As) with iPr₂PAcenapLi (Acenap = acenaphthene-5,6-diyl) afforded the thermally stable peri-substitution supported donor–acceptor complexes, iPr₂PAcenapEBr₂ 3 and 4. Both complexes show a strong P→E dative interaction, as observed by X-ray crystallography and ³¹P NMR spectroscopy. DFT calculations indicated the unusual As∙∙∙As contact (3.50 Å) observed in the solid state structure of 4 results from dispersion forces rather than metallic interactions. Incorporation of the excess AsBr₃ in the crystal structure of 3 promotes the formation of the ion separated species [iPr₂PAcenapAsBr]⁺Br⁻ 5. A decomposition product 6 containing the rare [As₆Br₈]^2– heterocubane dianion was isolated and characterised crystallographically. The reaction between iPr₂PAcenapLi and EtAsI₂ afforded tertiary arsine (BrAcenap)₂AsEt 7, which was subsequently lithiated and reacted with PhPCl₂ and Ph₂PCl to afford cyclic PhP(Acenap)₂AsEt 8 and acyclic EtAs(AcenapPPh₂)₂ 9

Original language	English
Article number	7222
Journal	Molecules
Volume	26
Issue number	23
DOIs	https://doi.org/10.3390/molecules26237222
Publication status	Published - 28 Nov 2021

Keywords

Single crystal X-ray structures
Arsenic
Peri-substitution
Organophosphorus
Pnictine

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Synthetic and Structural Study of peri-Substituted Phosphine-Arsines (dataset)
Kilian, P. (Creator), Chalmers, B. A. (Data Collector), Somisara, U. (Data Collector), Surgenor, B. A. (Contributor), Athukorala Arachchige, K. S. (Data Collector), Woollins, J. D. (Contributor), Buehl, M. (Contributor) & Slawin, A. M. Z. (Data Collector), University of St Andrews, 29 Nov 2021
DOI: 10.17630/7bae9495-1422-4bae-aa2b-d160ce8c1d3f
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@article{033c693f09004cbb8f83e97596362495,

title = "Synthetic and structural study of peri-substituted phosphine-arsines",

abstract = "A series of phosphorus-arsenic peri-substituted acenaphthene species have been isolated and fully characterised, including single crystal X-ray diffraction. Reactions of EBr3 (E = P, As) with iPr2PAcenapLi (Acenap = acenaphthene-5,6-diyl) afforded the thermally stable peri-substitution supported donor–acceptor complexes, iPr2PAcenapEBr2 3 and 4. Both complexes show a strong P→E dative interaction, as observed by X-ray crystallography and 31P NMR spectroscopy. DFT calculations indicated the unusual As∙∙∙As contact (3.50 {\AA}) observed in the solid state structure of 4 results from dispersion forces rather than metallic interactions. Incorporation of the excess AsBr3 in the crystal structure of 3 promotes the formation of the ion separated species [iPr2PAcenapAsBr]+Br− 5. A decomposition product 6 containing the rare [As6Br8]2– heterocubane dianion was isolated and characterised crystallographically. The reaction between iPr2PAcenapLi and EtAsI2 afforded tertiary arsine (BrAcenap)2AsEt 7, which was subsequently lithiated and reacted with PhPCl2 and Ph2PCl to afford cyclic PhP(Acenap)2AsEt 8 and acyclic EtAs(AcenapPPh2)2 9",

keywords = "Single crystal X-ray structures, Arsenic, Peri-substitution, Organophosphorus, Pnictine",

author = "Chalmers, {Brian A.} and Upulani Somisara and Surgenor, {Brian Andrew} and {Athukorala Arachchige}, {Kasun S.} and Woollins, {J Derek} and Michael Buehl and Slawin, {Alexandra M. Z.} and Petr Kilian",

note = "The authors thank the Engineering and Physical Sciences Research Council (EPSRC, Grant EP/J500549/1 and EP/M506631/1), COST action CM1302 SIPs and CM0802, and the EaStCHEM School of Chemistry for support. ",

year = "2021",

month = nov,

day = "28",

doi = "10.3390/molecules26237222",

language = "English",

volume = "26",

journal = "Molecules",

issn = "1420-3049",

publisher = "Multidisciplinary Digital Publishing Institute (MDPI)",

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TY - JOUR

T1 - Synthetic and structural study of peri-substituted phosphine-arsines

AU - Chalmers, Brian A.

AU - Somisara, Upulani

AU - Surgenor, Brian Andrew

AU - Athukorala Arachchige, Kasun S.

AU - Woollins, J Derek

AU - Buehl, Michael

AU - Slawin, Alexandra M. Z.

AU - Kilian, Petr

N1 - The authors thank the Engineering and Physical Sciences Research Council (EPSRC, Grant EP/J500549/1 and EP/M506631/1), COST action CM1302 SIPs and CM0802, and the EaStCHEM School of Chemistry for support.

PY - 2021/11/28

Y1 - 2021/11/28

N2 - A series of phosphorus-arsenic peri-substituted acenaphthene species have been isolated and fully characterised, including single crystal X-ray diffraction. Reactions of EBr3 (E = P, As) with iPr2PAcenapLi (Acenap = acenaphthene-5,6-diyl) afforded the thermally stable peri-substitution supported donor–acceptor complexes, iPr2PAcenapEBr2 3 and 4. Both complexes show a strong P→E dative interaction, as observed by X-ray crystallography and 31P NMR spectroscopy. DFT calculations indicated the unusual As∙∙∙As contact (3.50 Å) observed in the solid state structure of 4 results from dispersion forces rather than metallic interactions. Incorporation of the excess AsBr3 in the crystal structure of 3 promotes the formation of the ion separated species [iPr2PAcenapAsBr]+Br− 5. A decomposition product 6 containing the rare [As6Br8]2– heterocubane dianion was isolated and characterised crystallographically. The reaction between iPr2PAcenapLi and EtAsI2 afforded tertiary arsine (BrAcenap)2AsEt 7, which was subsequently lithiated and reacted with PhPCl2 and Ph2PCl to afford cyclic PhP(Acenap)2AsEt 8 and acyclic EtAs(AcenapPPh2)2 9

AB - A series of phosphorus-arsenic peri-substituted acenaphthene species have been isolated and fully characterised, including single crystal X-ray diffraction. Reactions of EBr3 (E = P, As) with iPr2PAcenapLi (Acenap = acenaphthene-5,6-diyl) afforded the thermally stable peri-substitution supported donor–acceptor complexes, iPr2PAcenapEBr2 3 and 4. Both complexes show a strong P→E dative interaction, as observed by X-ray crystallography and 31P NMR spectroscopy. DFT calculations indicated the unusual As∙∙∙As contact (3.50 Å) observed in the solid state structure of 4 results from dispersion forces rather than metallic interactions. Incorporation of the excess AsBr3 in the crystal structure of 3 promotes the formation of the ion separated species [iPr2PAcenapAsBr]+Br− 5. A decomposition product 6 containing the rare [As6Br8]2– heterocubane dianion was isolated and characterised crystallographically. The reaction between iPr2PAcenapLi and EtAsI2 afforded tertiary arsine (BrAcenap)2AsEt 7, which was subsequently lithiated and reacted with PhPCl2 and Ph2PCl to afford cyclic PhP(Acenap)2AsEt 8 and acyclic EtAs(AcenapPPh2)2 9

KW - Single crystal X-ray structures

KW - Arsenic

KW - Peri-substitution

KW - Organophosphorus

KW - Pnictine

U2 - 10.3390/molecules26237222

DO - 10.3390/molecules26237222

M3 - Article

SN - 1420-3049

VL - 26

JO - Molecules

JF - Molecules

IS - 23

M1 - 7222

ER -

Synthetic and structural study of peri-substituted phosphine-arsines

Abstract

Keywords

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Datasets

Synthetic and Structural Study of peri-Substituted Phosphine-Arsines (dataset)

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