Low‐Temperature Isolation of the Bicyclic Phosphinophosphonium Salt [Mes*₂P₄Cl][GaCl₄]

Abstract

The reaction of [ClP(μ-PMes*)]2 (1) with the Lewis acid GaCl3 yielded a hitherto unknown tetraphosphabicyclo[1.1.0]butan-2-ium salt, [Mes*P4(Cl)Mes*][GaCl4] (3[GaCl4]), which incorporates a positively charged phosphonium center within its bicyclic P4 scaffold. The formation of the title compound was studied by means of low-temperature NMR experiments. This led to the identification of an intermediate cyclotetraphosphenium cation, which was trapped by reaction with dimethylbutadiene (dmb). All of the compounds were fully characterized by experimental and computational methods.

A Gallium‐Substituted Distibene and an Antimony‐Analogue Bicyclo[1.1.0]butane: Synthesis and Solid‐State Structures

“…[36] Analogous dicationic compounds of the lighter homologues Pa nd As,s uch as [(Ph 3 E) 2 P 4 ] 2+ (E = P, As) and the bicyclicp hosphinophosphonium monocationic [Mes* 2 P 4 Cl] + , as well as the Lewis acid-stabilized version of the RP 4 anion have also recently been structurally characterized. [37][38][39] [(Me 3 P) 4 [40] To our knowledge,M es* 2 P 2 Sb 2 is the only structurally characterized Sb-containing bicyclo[1.1.0]butane derivative. [41] It was formed by reaction of Cp*SbCl 2 with Mes*P(SiMe 3 )Li, through the formation of stibaphosphene Cp*Sb = PMes* as an intermediate,which undergoes Cp*ÀSb bond cleavage and formation of aradical, which further reacts under SbÀSb bond formation.…”

A Systematic Survey of the Reactivity of Chlorinated N2P2, NP3 and P4 Ring Systems

“…This is corroborated by the fact that the isomerization of the tetraphosphenium salt 7 to the bicyclic isomer 8 proceeded even at À80 8C. [32] As with the P 4 congener 7,all attempts to crystallize the azatriphosphenium salt 6 at low temperatures remained unsuccessful. In two instances, af ew crystalso ft wo different decompositionp roducts could be isolateda nd studied by single crystal X-ray diffraction (SC-XRD).…”

“…For each species,atotal of about 45 resonance structures was considered, most of which describe bond polarization within the ring or negative hyperconjugation of the LPs at Cl into the ring system. To simplifyt he discussion, only the two most important contributions to the Lewis resonance Scheme,a sw ell as the Lewis structure with an electron sextet at the formal Scheme7.ReactionofN P 3 ring system 2 with GaCl 3 (R = Mes*), in comparison with the reactivities of P 4 and N 2 P 2 ring systems 3 (R = Mes*) [32] and 9 (R = Te r = 2,6-dimesitylphenyl). [23] phosphenium centre will be considered in the following (Scheme 9).…”

Anorganische Molekülchemie

“…Wird [ClP(µ-PMes*)] 2 mit der Lewis-Säure GaCl 3 umgesetzt, entsteht das bicyclische Triphosphinophosphoniumkation als exo-exo-(63) und endo-exo-Isomer, bei dem der verbleibende Chloridligand an ein Mes*-substituiertes Phosphoratom bindet. 62 80) Um nichtkovalente Wechselwirkung zwischen Gruppe-18-Elementen und Elektronendonoren wie Lewis-Basen oder Anionen zu beschreiben, dient das aerogene Bindungskonzept. Das auf dem σ-Loch-Ansatz basierende Konzept ergibt sich aus Ab-initio-Berechnungen von Xenonspezies und ergibt Beiträge zur Bindungsenergie, die anderen, bereits bekannten σ-Loch-Wechselwirkungen ähneln, wenngleich aerogene Bindungen weniger gerichtet sind.…”