Phosphorus‒bismuth peri-substituted acenaphthenes: a synthetic, structural and computational study

Phillip Nejman; Thomasine Emily Curzon; Michael Buehl; David McKay; J Derek Woollins; Sharon E. Ashbrook; David Bradford Cordes; Alexandra Martha Zoya Slawin; Petr Kilian

doi:10.1021/acs.inorgchem.0c00317

Phosphorus‒bismuth peri-substituted acenaphthenes: a synthetic, structural and computational study

Phillip Nejman, Thomasine Emily Curzon, Michael Buehl, David McKay, J Derek Woollins, Sharon E. Ashbrook, David Bradford Cordes, Alexandra Martha Zoya Slawin, Petr Kilian

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

Abstract

A series of acenaphthene species with a diisopropylphosphino group and a variety of bismuth functionalities in the peri-positions were synthesised and fully characterised, including single crystal X–ray diffraction. The majority of the reported species feature a relatively rare interpnictogen P−Bi bond. The series includes the phosphine¬−bismuthine, Acenap(PiPr₂)(BiPh₂) 2 (Acenap = acenaphthene-5,6-diyl), which was subjected to a fluorodearylation reaction to produce Acenap(PiPr₂)(BiPhX) 5−8 and 10 (X = BF₄^-, Cl, Br, I, SPh), displaying varying degrees of ionicity. The geminally bis(acenaphthyl) substituted [Acenap(PiPr₂)₂]BiPh 3 shows a large through-space coupling of 17.8 Hz, formally ^8TS_JPP. Coupling deformation density (CDD) calculations confirm the double through-space coupling pathway, in which the P and Bi lone pairs mediate communication between the two ³¹P nuclei. Several synthetic routes towards the phosphine−diiodobismuthine Acenap(PiPr₂)(BiI₂) 9 have been investigated, however the purity of this, surprisingly thermally stable potential synthon, remains poor.

Original language	English
Journal	Inorganic Chemistry
Volume	Article ASAP
Early online date	9 Apr 2020
DOIs	https://doi.org/10.1021/acs.inorgchem.0c00317
Publication status	E-pub ahead of print - 9 Apr 2020

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10.1021/acs.inorgchem.0c00317

Main paper v39 revised
Copyright © 2020 American Chemical Society. This work has been made available online in accordance with publisher policies or with permission. Permission for further reuse of this content should be sought from the publisher or the rights holder. This is the author created accepted manuscript following peer review and may differ slightly from the final published version. The final published version of this work is available at https://doi.org/10.1021/acs.inorgchem.0c00317
Accepted author manuscript, 1.03 MB
Supporting_Info_v9Accepted author manuscript, 920 KB

CRITICAT CDT: Critical Resource Catalysis - CRITICAT
Smith, A. D. (PI), Nolan, S. P. (CoI) & Westwood, N. J. (CoI)
EPSRC
1/05/14 → 31/10/22
Project: Standard

Phosphorus‒Bismuth peri-Substituted Acenaphthenes: A Synthetic, Structural and Computational Study (dataset)
Kilian, P. (Creator), Buehl, M. (Contributor) & McKay, D. (Contributor), University of St Andrews, 10 Apr 2020
DOI: 10.17630/39edc339-fbac-402e-9034-cfaa44a34251
Dataset

File
Phosphorus‒Bismuth peri-Substituted Acenaphthenes: A Synthetic, Structural and Computational Study (crystallographic dataset)
Curzon, T. E. (Creator), Buehl, M. (Creator), McKay, D. (Creator), Ashbrook, S. E. M. (Creator), Cordes, D. B. (Creator), Slawin, A. M. Z. (Creator) & Kilian, P. (Creator), Cambridge Crystallographic Data Centre, 2020
https://dx.doi.org/10.5517/ccdc.csd.cc23d6k9 and 9 more links, https://dx.doi.org/10.5517/ccdc.csd.cc23d6lb, https://dx.doi.org/10.5517/ccdc.csd.cc23d6g6, https://dx.doi.org/10.5517/ccdc.csd.cc23d6qg, https://dx.doi.org/10.5517/ccdc.csd.cc23d6f5, https://dx.doi.org/10.5517/ccdc.csd.cc23d6nd, https://dx.doi.org/10.5517/ccdc.csd.cc23d6h7, https://dx.doi.org/10.5517/ccdc.csd.cc23d6j8, https://dx.doi.org/10.5517/ccdc.csd.cc23d6mc, https://dx.doi.org/10.5517/ccdc.csd.cc23d6pf (show fewer)
Dataset

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title = "Phosphorus‒bismuth peri-substituted acenaphthenes: a synthetic, structural and computational study",

abstract = "A series of acenaphthene species with a diisopropylphosphino group and a variety of bismuth functionalities in the peri-positions were synthesised and fully characterised, including single crystal X–ray diffraction. The majority of the reported species feature a relatively rare interpnictogen P−Bi bond. The series includes the phosphine¬−bismuthine, Acenap(PiPr2)(BiPh2) 2 (Acenap = acenaphthene-5,6-diyl), which was subjected to a fluorodearylation reaction to produce Acenap(PiPr2)(BiPhX) 5−8 and 10 (X = BF4-, Cl, Br, I, SPh), displaying varying degrees of ionicity. The geminally bis(acenaphthyl) substituted [Acenap(PiPr2)2]BiPh 3 shows a large through-space coupling of 17.8 Hz, formally 8TSJPP. Coupling deformation density (CDD) calculations confirm the double through-space coupling pathway, in which the P and Bi lone pairs mediate communication between the two 31P nuclei. Several synthetic routes towards the phosphine−diiodobismuthine Acenap(PiPr2)(BiI2) 9 have been investigated, however the purity of this, surprisingly thermally stable potential synthon, remains poor.",

author = "Phillip Nejman and Curzon, {Thomasine Emily} and Michael Buehl and David McKay and Woollins, {J Derek} and Ashbrook, {Sharon E.} and Cordes, {David Bradford} and Slawin, {Alexandra Martha Zoya} and Petr Kilian",

note = "This work was financially supported by the Engineering and Physical Sciences Research Council (EPSRC). This included PhD studentship to TEC (Centre for Doctoral Training in Critical Resource Catalysis (CRITICAT), Grant code: EP/L016419/1) and to PN (Grant code EP/L505079/1). The authors would like to thank COST action SM1302 SIPs; the EPSRC UK National Mass Spectrometry Facility at Swansea University for the acquisition and processing of Mass Spectrometry Data and to EaStCHEM and the School of Chemistry for support. ",

year = "2020",

month = apr,

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doi = "10.1021/acs.inorgchem.0c00317",

language = "English",

volume = "Article ASAP",

journal = "Inorganic Chemistry",

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publisher = "American Chemical Society (ACS)",

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TY - JOUR

T1 - Phosphorus‒bismuth peri-substituted acenaphthenes

T2 - a synthetic, structural and computational study

AU - Nejman, Phillip

AU - Curzon, Thomasine Emily

AU - Buehl, Michael

AU - McKay, David

AU - Woollins, J Derek

AU - Ashbrook, Sharon E.

AU - Cordes, David Bradford

AU - Slawin, Alexandra Martha Zoya

AU - Kilian, Petr

N1 - This work was financially supported by the Engineering and Physical Sciences Research Council (EPSRC). This included PhD studentship to TEC (Centre for Doctoral Training in Critical Resource Catalysis (CRITICAT), Grant code: EP/L016419/1) and to PN (Grant code EP/L505079/1). The authors would like to thank COST action SM1302 SIPs; the EPSRC UK National Mass Spectrometry Facility at Swansea University for the acquisition and processing of Mass Spectrometry Data and to EaStCHEM and the School of Chemistry for support.

PY - 2020/4/9

Y1 - 2020/4/9

N2 - A series of acenaphthene species with a diisopropylphosphino group and a variety of bismuth functionalities in the peri-positions were synthesised and fully characterised, including single crystal X–ray diffraction. The majority of the reported species feature a relatively rare interpnictogen P−Bi bond. The series includes the phosphine¬−bismuthine, Acenap(PiPr2)(BiPh2) 2 (Acenap = acenaphthene-5,6-diyl), which was subjected to a fluorodearylation reaction to produce Acenap(PiPr2)(BiPhX) 5−8 and 10 (X = BF4-, Cl, Br, I, SPh), displaying varying degrees of ionicity. The geminally bis(acenaphthyl) substituted [Acenap(PiPr2)2]BiPh 3 shows a large through-space coupling of 17.8 Hz, formally 8TSJPP. Coupling deformation density (CDD) calculations confirm the double through-space coupling pathway, in which the P and Bi lone pairs mediate communication between the two 31P nuclei. Several synthetic routes towards the phosphine−diiodobismuthine Acenap(PiPr2)(BiI2) 9 have been investigated, however the purity of this, surprisingly thermally stable potential synthon, remains poor.

AB - A series of acenaphthene species with a diisopropylphosphino group and a variety of bismuth functionalities in the peri-positions were synthesised and fully characterised, including single crystal X–ray diffraction. The majority of the reported species feature a relatively rare interpnictogen P−Bi bond. The series includes the phosphine¬−bismuthine, Acenap(PiPr2)(BiPh2) 2 (Acenap = acenaphthene-5,6-diyl), which was subjected to a fluorodearylation reaction to produce Acenap(PiPr2)(BiPhX) 5−8 and 10 (X = BF4-, Cl, Br, I, SPh), displaying varying degrees of ionicity. The geminally bis(acenaphthyl) substituted [Acenap(PiPr2)2]BiPh 3 shows a large through-space coupling of 17.8 Hz, formally 8TSJPP. Coupling deformation density (CDD) calculations confirm the double through-space coupling pathway, in which the P and Bi lone pairs mediate communication between the two 31P nuclei. Several synthetic routes towards the phosphine−diiodobismuthine Acenap(PiPr2)(BiI2) 9 have been investigated, however the purity of this, surprisingly thermally stable potential synthon, remains poor.

U2 - 10.1021/acs.inorgchem.0c00317

DO - 10.1021/acs.inorgchem.0c00317

M3 - Article

SN - 0020-1669

VL - Article ASAP

JO - Inorganic Chemistry

JF - Inorganic Chemistry

ER -

Phosphorus‒bismuth peri-substituted acenaphthenes: a synthetic, structural and computational study

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CRITICAT CDT: Critical Resource Catalysis - CRITICAT

Datasets

Phosphorus‒Bismuth peri-Substituted Acenaphthenes: A Synthetic, Structural and Computational Study (dataset)

Phosphorus‒Bismuth peri-Substituted Acenaphthenes: A Synthetic, Structural and Computational Study (crystallographic dataset)

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