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| Naji, M. |
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| Motta, Antonella |
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| Aletan, Dirar |
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| Mohamed, Tarek |
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| Ertürk, Emre |
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| Taccardi, Nicola |
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| Kononenko, Denys |
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| Petrov, R. H. | Madrid |
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| Alshaaer, Mazen | Brussels |
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| Bih, L. |
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| Casati, R. |
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| Muller, Hermance |
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| Kočí, Jan | Prague |
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| Šuljagić, Marija |
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| Kalteremidou, Kalliopi-Artemi | Brussels |
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| Azam, Siraj |
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| Ospanova, Alyiya |
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| Blanpain, Bart |
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| Ali, M. A. |
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| Popa, V. |
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| Rančić, M. |
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| Ollier, Nadège |
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| Azevedo, Nuno Monteiro |
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| Landes, Michael |
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| Rignanese, Gian-Marco |
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Chalmers, Brian Alexander
University of St Andrews
in Cooperation with on an Cooperation-Score of 37%
Topics
Publications (8/8 displayed)
- 2021Synthetic and structural study of peri-substituted phosphine-arsinescitations
- 2018A study of through-space and through-bond JPP coupling in a rigid nonsymmetrical bis(phosphine) and its metal complexescitations
- 2016Rhodium(III) and iridium(III) half-sandwich complexes with tertiary arsine and stibine ligandscitations
- 2016Peri-substituted phosphorus-tellurium systems – an experimental and theoretical investigation of the P∙∙∙Te through-space interactioncitations
- 2015Rhodium(III) and iridium(III) half-sandwich complexes with tertiary arsine and stibine ligandscitations
- 2015A synthetic, spectroscopic and structural examination of phosphorus, arsenic and antimony peri-substituted acenaphthenes
- 2015Peri-substituted phosphorus-tellurium systems – an experimental and theoretical investigation of the P∙∙∙Te through-space interactioncitations
- 2015Peri-substituted phosphorus-tellurium systems – an experimental and theoretical investigation of the P∙∙∙Te through-space interactioncitations
Places of action
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article
Synthetic and structural study of peri-substituted phosphine-arsines
Abstract
A series of phosphorus-arsenic peri-substitutedacenaphthene species have been isolated and fully characterised,including single crystal X-ray diffraction. Reactions of EBr<sub>3</sub> (E = P, As) with iPr<sub>2</sub>PAcenapLi (Acenap = acenaphthene-5,6-diyl) afforded the thermally stable peri-substitution supported donor–acceptor complexes, iPr<sub>2</sub>PAcenapEBr<sub>2</sub><b> 3</b> and <b>4</b>. Both complexes show a strong P→E dative interaction, as observed by X-ray crystallography and <sup>31</sup>P NMR spectroscopy. DFT calculations indicated the unusual As∙∙∙As contact (3.50 Å) observed in the solid state structure of <b>4</b> results from dispersion forces rather than metallic interactions. Incorporation of the excess AsBr<sub>3</sub> in the crystal structure of <b>3</b> promotes the formation of the ion separated species [iPr<sub>2</sub>PAcenapAsBr]<sup>+</sup>Br<sup>−</sup> <b>5</b>. A decomposition product <b>6</b> containing the rare [As<sub>6</sub>Br<sub>8</sub>]<sup>2–</sup> heterocubane dianion was isolated and characterised crystallographically. The reaction between iPr<sub>2</sub>PAcenapLi and EtAsI<sub>2</sub> afforded tertiary arsine (BrAcenap)<sub>2</sub>AsEt <b>7</b>, which was subsequently lithiated and reacted with PhPCl<sub>2</sub> and Ph<sub>2</sub>PCl to afford cyclic PhP(Acenap)<sub>2</sub>AsEt <b>8</b> and acyclic EtAs(AcenapPPh<sub>2</sub>)<sub>2</sub> <b>9</b>