Frötschel-Rittmeyer Julia, Holthausen Michael, Friedmann Christian, Röhner David, Krossing Ingo, Weigand Jan J
Faculty of Chemistry and Food Chemistry, Technische Universität Dresden, 01062 Dresden, Germany.
Institut für Anorganische und Analytische Chemie and Freiburg Materials Research Center FMF, Albert-Ludwigs-Universität Freiburg, Albertstrasse 21, 79104 Freiburg, Germany.
Sci Adv. 2022 Sep 9;8(36):eabq8613. doi: 10.1126/sciadv.abq8613. Epub 2022 Sep 7.
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]. Apparently, the nido-cation [P] forms intermediately in all reactions, particularly during the Ga(I)-induced reduction of [PCl] and the subsequent pick up of P to yield the final salt [P][GaCl]. The solid-state structure of [P][GaCl] reveals the anticipated -symmetric Zintl-type cage for the [P] cation. Our approaches show great potential to bring other [P] cations from the gas to the condensed phase.
最近针对一系列[P]盐（= [F{Al(OR)}]、[Al(OR)]和(R = C(CF)); GaCl）的合成方法克服了经典合成方法中被证明不适用于磷阳离子的局限性。这些盐通过以下方式含有同多原子阳离子[P]：（I）用NO[F{Al(OR)}]氧化P；（II）芳烃稳定的Co(I)夹心配合物[Co(芳烃)][Al(OR)] [芳烃 = -二氟苯(-DFB)和氟苯(FB)]；或（III）在P存在下，以Ga[GaCl]作为Ga(I)源还原[PCl][GaCl]。量子化学CCSD(T)计算表明，[Co(芳烃)]形成[P]是通过类巢型簇[(-DFB)CoP]，它类似于等电子的、难以捉摸的[P]。显然，类巢阳离子[P]在所有反应中都中间形成，特别是在Ga(I)诱导的[PCl]还原以及随后夺取P以生成最终盐[P][GaCl]的过程中。[P][GaCl]的固态结构揭示了[P]阳离子预期的 -对称津特耳型笼状结构。我们的方法显示出将其他[P]阳离子从气相引入凝聚相的巨大潜力。
