Synthesis and Characterisation oftetrahedro-Tetraphosphorus Complexes of Rhenium – Evidence for the First Bridging Complex of White Phosphorus

Reaction of white phosphorus with [(triphos)Re(CO)2(OTf)] (1) in dichloromethane affords the new tetraphosphorus complex [(triphos)Re(CO)2(η1-P4)](OTf) (2) [triphos = MeC(CH2PPh2)3; OTf = OSO2CF3]. Compound 2 reacts with a second equivalent of 1 to give the binuclear complex [{(triphos)Re(CO)2}2(μ,η1,η1-P4)](OTf)2 (3) in which a tetrahedro-P4 ligand behaves as tethering unit between two [(triphos)Re(CO)2]+ moieties. Complexes 2 and 3 represent the first soluble metal complexes of the tetraphosphorus molecule where the P4 ligand has not undergone any major modification.