White phosphorus as a ligand for the coinage metalsElectronic supplementary information (ESI) available: Syntheses and experimental data for 13 and a detailed discussion of computational methods used. CCDC 841996, 841997 and 841998. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c2cc15291f

Reaction of equimolar quantities of MX (M = Au, Cu, X = Cl; M = Ag, X = OTf) and GaCl 3 in CH 2 Cl 2 with P 4 leads to phosphorus ligating a cationic coinage metal centre. For Cu and Ag, ion-contacted coordination polymers are formed; for Au, an ion-separated complex is observed that features the [Au( 2 -P 4 ) 2 ] + cation, which is the first homoleptic AuP 4 complex to be characterised in the condensed phase. The interactions of P 4 with cationic coinage metal centres are studied. For Cu and Ag, ion-contacted coordination polymers are formed; for Au, an ion-separated complex is observed that features the [Au( 2 -P 4 ) 2 ] + cation.