A series of phosphorus-arsenic
peri-substituted acenaphthene species have been isolated and fully characterised, including single crystal X-ray diffraction. Reactions of EBr
3 (E = P, As) with
iPr
2PAcenapLi (Acenap = acenaphthene-5,6-diyl) afforded the thermally stable
peri-substitution supported donor–acceptor
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A series of phosphorus-arsenic
peri-substituted acenaphthene species have been isolated and fully characterised, including single crystal X-ray diffraction. Reactions of EBr
3 (E = P, As) with
iPr
2PAcenapLi (Acenap = acenaphthene-5,6-diyl) afforded the thermally stable
peri-substitution supported donor–acceptor complexes,
iPr
2PAcenapEBr
23 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 AsBr
3 in the crystal structure of
3 promotes the formation of the ion separated species [
iPr
2PAcenapAsBr]
+Br
− 5. A decomposition product
6 containing the rare [As
6Br
8]
2– heterocubane dianion was isolated and characterised crystallographically. The reaction between
iPr
2PAcenapLi and EtAsI
2 afforded tertiary arsine (BrAcenap)
2AsEt
7, which was subsequently lithiated and reacted with PhPCl
2 and Ph
2PCl to afford cyclic PhP(Acenap)
2AsEt
8 and acyclic EtAs(AcenapPPh
2)
2 9.
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