Coordination and reactivity of white phosphorus and tetraphosphorus trisulphide in the presence of the fragment CpFe(dppe) [dppe = 1,2-bis(diphenylphosphino)ethane]

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.

Graphical abstractThe monometallic [CpFe(dppe)(η1-P4)]PF6, [CpFe(dppe)(η1-Pbasal-P4S3)]OTf, and the bimetallic compounds [{CpFe(dppe)}2(μ,η1:1-P4)](PF6)2 and [{CpFe(dppe)}2(μ,η1:1-Papical-Pbasal-P4S3)](OTf)2, containing the P4 or the P4S3 molecules bound to one or two CpFe(dppe) fragments through phosphorus atom(s), have been synthesized and characterized. The coordinated molecules easily react with water at room temperature and the reaction products have been identified.Figure optionsDownload full-size imageDownload as PowerPoint slide