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

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Date
09/04/2020
Author
Nejman, Phillip
Curzon, Thomasine Emily
Buehl, Michael
McKay, David
Woollins, J Derek
Ashbrook, Sharon E.
Cordes, David Bradford
Slawin, Alexandra Martha Zoya
Kilian, Petr
Funder
EPSRC
Grant ID
EP/L016419/1
Keywords
QD Chemistry
DAS
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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.
Citation
Nejman , P , Curzon , T E , Buehl , M , McKay , D , Woollins , J D , Ashbrook , S E , Cordes , D B , Slawin , A M Z & Kilian , P 2020 , ' Phosphorus‒bismuth peri -substituted acenaphthenes : a synthetic, structural and computational study ' , Inorganic Chemistry , vol. Article ASAP . https://doi.org/10.1021/acs.inorgchem.0c00317
Publication
Inorganic Chemistry
Status
Peer reviewed
DOI
https://doi.org/10.1021/acs.inorgchem.0c00317
ISSN
0020-1669
Type
Journal article
Rights
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
Description
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.
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  • University of St Andrews Research
URI
http://hdl.handle.net/10023/22991

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