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First experimental evidence for the elusive tetrahedral cations [EP3]+ (E = S, Se, Te) in the condensed phase.

ABSTRACT: Condensed phase access to the unprecedented tetrahedral cations [EP3]+ (E = S, Se, Te) was achieved through the reaction of ECl3[WCA] with white phosphorus ([WCA]- = [Al(ORF)4]- and [F(Al(ORF)3)2]-; -RF = -C(CF3)3). Previously, [EP3]+ was only known from gas phase MS investigations. By contrast, the reaction of ECl3[A] with the known P3 3- synthon Na[Nb(ODipp)3(P3)] (enabling AsP3 synthesis), led to formation of P4. The cations [EP3]+ were characterized by multinuclear NMR spectroscopy in combination with high-level quantum chemical calculations. Their bonding situation is described with several approaches including Atoms in Molecules and Natural Bond Orbital analysis. The first series of well-soluble salts ECl3[WCA] was synthesized and fully characterized as starting materials for the studies on this elusive class of [EP3]+ cations. Yet, with high [ECl3]+ fluoride ion affinity values between 775 (S), 803 (Se) and 844 (Te) kJ mol-1, well exceeding typical phosphenium ions, these well-soluble ECl3[WCA] salts could be relevant in view of the renewed interest in strong (also cationic) Lewis acids.

SUBMITTER: Weis P 

PROVIDER: S-EPMC7006506 | biostudies-literature | 2019 Dec

REPOSITORIES: biostudies-literature

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First experimental evidence for the elusive tetrahedral cations [EP<sub>3</sub>]<sup>+</sup> (E = S, Se, Te) in the condensed phase.

Weis Philippe P   Röhner David Christopher DC   Prediger Richard R   Butschke Burkhard B   Scherer Harald H   Weber Stefan S   Krossing Ingo I  

Chemical science 20191007 46

Condensed phase access to the unprecedented tetrahedral cations [EP<sub>3</sub>]<sup>+</sup> (E = S, Se, Te) was achieved through the reaction of ECl<sub>3</sub>[WCA] with white phosphorus ([WCA]<sup>-</sup> = [Al(OR<sup>F</sup>)<sub>4</sub>]<sup>-</sup> and [F(Al(OR<sup>F</sup>)<sub>3</sub>)<sub>2</sub>]<sup>-</sup>; -R<sup>F</sup> = -C(CF<sub>3</sub>)<sub>3</sub>). Previously, [EP<sub>3</sub>]<sup>+</sup> was only known from gas phase MS investigations. By contrast, the reaction of ECl<sub>3</  ...[more]

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