Positive at last: The first condensed-phase homopolyatomic phosphorus cation [P(9)](+) was prepared using a combination of the oxidant [NO](+) and weakly coordinating anion, [Al{OC(CF(3))(3)}(4)](-). [P(9)](+) consists of two P(5) cages linked by a phosphonium atom to give a D(2d)-symmetric Zintl cluster. NMR (see picture), Raman, and IR spectroscopy, mass spectrometry, and quantum-chemical calculations confirmed the structure.
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Homoatomic cations: From [P] to [P].
Sci Adv
September 2022
Faculty of Chemistry and Food Chemistry, Technische Universität Dresden, 01062 Dresden, Germany.
Recent synthetic approaches to a series of [P] salts ( = [F{Al(OR)}], [Al(OR)], and (R = C(CF)); GaCl) overcome limitations in classical synthesis methods that proved unsuitable for phosphorus cations. These salts contain the homopolyatomic cation [P] via (I) oxidation of P with NO[F{Al(OR)}], (II) the arene-stabilized Co(I) sandwich complex [Co(arene)][Al(OR)] [arene = -difluorobenzene (-DFB) and fluorobenzene (FB)], or (III) the reduction of [PCl][GaCl] with Ga[GaCl] as Ga(I) source in the presence of P. Quantum chemical CCSD(T) calculations suggest that [P] formation from [Co(arene)] occurs via the nido-type cluster [(-DFB)CoP], which resembles the isoelectronic, elusive [P].
View Article and Find Full Text PDF[P9]+ [Al(OR(F))4)]-, the salt of a homopolyatomic phosphorus cation.
Angew Chem Int Ed Engl
June 2012
Institut für Anorganische und Analytische Chemie, Freiburger Materialforschungszentrum (FMF), Albert-Ludwigs-Universität Freiburg, Germany.
Positive at last: The first condensed-phase homopolyatomic phosphorus cation [P(9)](+) was prepared using a combination of the oxidant [NO](+) and weakly coordinating anion, [Al{OC(CF(3))(3)}(4)](-). [P(9)](+) consists of two P(5) cages linked by a phosphonium atom to give a D(2d)-symmetric Zintl cluster. NMR (see picture), Raman, and IR spectroscopy, mass spectrometry, and quantum-chemical calculations confirmed the structure.
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