Homoatomic cations: From [P<sub>5</sub>]<sup>+</sup> to [P<sub>9</sub>]<sup></sup>.
basic_science · Level V
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- Record sourced from PubMed, PMID 36070385.
- Also identified by DOI 10.1126/sciadv.abq8613 and PMC identifier 9451154.
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Abstract
Recent synthetic approaches to a series of [P<sub>9</sub>]<i>X</i> salts (<i>X</i> = [F{Al(OR<sup>F</sup>)<sub>3</sub>}<sub>2</sub>], [Al(OR<sup>F</sup>)<sub>4</sub>], and (R<sup>F</sup> = C(CF<sub>3</sub>)<sub>3</sub>); Ga<sub>2</sub>Cl<sub>7</sub>) overcome limitations in classical synthesis methods that proved unsuitable for phosphorus cations. These salts contain the homopolyatomic cation [P<sub>9</sub>]<sup>+</sup> via (I) oxidation of P<sub>4</sub> with NO[F{Al(OR<sup>F</sup>)<sub>3</sub>}<sub>2</sub>], (II) the arene-stabilized Co(I) sandwich complex [Co(arene)<sub>2</sub>][Al(OR<sup>F</sup>)<sub>4</sub>] [arene = <i>ortho</i>-difluorobenzene (<i>o</i>-DFB) and fluorobenzene (FB)], or (III) the reduction of [P<sub>5</sub>Cl<sub>2</sub>][Ga<sub>2</sub>Cl<sub>7</sub>] with Ga[Ga<sub>2</sub>Cl<sub>7</sub>] as Ga(I) source in the presence of P<sub>4</sub>. Quantum chemical CCSD(T) calculations suggest that [P<sub>9</sub>]<sup>+</sup> formation from [Co(arene)<sub>2</sub>]<sup>+</sup> occurs via the nido-type cluster [(<i>o</i>-DFB)CoP<sub>4</sub>]<sup>+</sup>, which resembles the isoelectronic, elusive [P<sub>5</sub>]<sup>+</sup>. Apparently, the nido-cation [P<sub>5</sub>]<sup>+</sup> forms intermediately in all reactions, particularly during the Ga(I)-induced reduction of [P<sub>5</sub>Cl<sub>2</sub>]<sup>+</sup> and the subsequent pick up of P<sub>4</sub> to yield the final salt [P<sub>9</sub>][Ga<sub>2</sub>Cl<sub>7</sub>]. The solid-state structure of [P<sub>9</sub>][Ga<sub>2</sub>Cl<sub>7</sub>] reveals the anticipated <i>D</i><sub>2d</sub>-symmetric Zintl-type cage for the [P<sub>9</sub>]<sup>+</sup> cation. Our approaches show great potential to bring other [P<i><sub>n</sub></i>]<sup>+</sup> cations from the gas to the condensed phase.