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Different reactions of Mes? substituted phosphanes (Mes? = 2,4,6-tri-tert-butylphenyl) led to the formation of the bicyclic tetraphosphane Mes?P4Mes? (5) and its unknown Lewis acid adduct 5·GaCl3. In this context, the endo-exo isomer

The reaction of [CpFe(dppe)Cl] (1) [dppe = 1,2-bis(diphenylphosphino)ethane] with one equivalent of P4 or P4S3 in the presence of a chloride scavenger, TlPF6 or AgOTf (OTf = triflate, OSO2CF3), affords the complexes [CpFe(dppe)(η1-P4)]PF6 (2) and [CpFe(dppe)(η1-Pbasal-P4S3)]OTf (3) which contain the tetrahedral P4 and the mixed P4S3 cage molecule η1-bound to the metal. Both P4 and P4S3 yield furthermore the dimetal compounds [{CpFe(dppe)}2(μ,η1:1-P4)](PF6)2 (4) and [{CpFe(dppe)}2(μ,η1:1-Papical-Pbasal-P4S3)](OTf)2 (5), which contain the tetrahedral P4 or the mixed-cage P4S3 molecule tethering two ruthenium fragments via two phosphorus atoms. All the compounds have been characterized by elemental analyses and NMR measurements. The crystal structure of 4 has been determined by X-ray diffraction methods. The complexes readily react with excess water under mild reaction conditions and the outcoming products have been identified.

Reactions of X2 (X = Br, I), P4 and Ag(CH2Cl2)[Al(OR)4] [R = C(CF3)3] in suitable ratios to prepare naked polyphosphorus cations were carried out and led to products which sugges

Insertion of the intermediately formed carbeneanaloguous PX2+ ion (X = Br, I) into one of the P-P bonds of the P4 tetrahedron led to the P5X2+ ion (see structure of the Br derivative)-the first example of the previously unknown class of phosphorus-rich binary P-X cations.