Homoatomic cations: From [P 5 ] + to [P 9 ] +

Publikation: Beitrag in FachzeitschriftForschungsartikelBeigetragenBegutachtung

Beitragende

Abstract

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

Details

OriginalspracheEnglisch
Aufsatznummereabq8613
FachzeitschriftScience advances
Jahrgang8
Ausgabenummer36
PublikationsstatusVeröffentlicht - 1 Sept. 2022
Peer-Review-StatusJa

Externe IDs

Scopus 85139415210
PubMed 36070385
Mendeley 49d907d8-fafb-32d1-941a-8c2e9fed02f3
ORCID /0000-0001-7323-7816/work/142257430

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