Superweak complexes of tetrahedral P4 molecules with the silver cation of weakly coordinating anions

The silver aluminates AgAl[OC(CF3)2(R)]4 (R = H, CH3, CF3) react with solutions of white phosphorus P4 to give complexes that bind one or two almost undistorted tetrahedral P4 molecules in an fashion: [Ag(P4)2]+[Al(OC(CF3)3)4]+ (1) containing the first homoleptic metal-phosphorus cation, the molecular species (P4)AgAl[OC(CH3)(CF3)2]4 (2), and the dimeric Ag(mu,eta2-P4)Ag bridged [(P4)AgAl[OC(H)(CF3)2]4]2 (3). Compounds 1-3 were characterized by variable-temperature (VT) 31P NMR spectroscopy (1 also by VT 32P MAS-NMR spectroscopy), Raman spectroscopy, and single-crystal X-ray crystallography. Other Ag:P4 ratios did not lead to new species, and this observation was rationalized on thermodynamic grounds. The Ag(P4)2+ ion has an almost planar coordination environment around the Ag+ ion due to d(x2 - y2)(Ag) --> sigma*(P-P) backbonding. Calculations (HF-DFT) on six Ag(P4)2+ isomers 4a-f showed that the planar eta2 form 4a is only slightly favored by 5.2 kJ mol(-1) over the tetrahedral eta2 species 4b; eta1-P4 and eta3-P4 complexes are less favorable (27-76 kJ mol(-1)). The bonding of the P4 moiety in [RhCl(eta2-P4)(PPh3)2], the only compound in which an eta2 bonding mode of a tetrahedral P4 molecule has been claimed, must be regarded as a tetraphosphabicyclobutane, and not as a tetrahedro-P4 complex, on the basis of the published NMR and vibrational spectra, the calculated geometry of [RhCl(P4)(PH3)2] (10), the highly endothermic (385 kJ mol(-1)) calculated dissociation enthalpy of 10 into P4 and RhCl(PH3)2 (11), as well as atoms in molecules (AIM) and natural bond orbital (NBO) population analyses of 10 and the Ag(P4)2+ ion. Therefore, 1-3 are the first examples of species containing eta2-coordinated tetrahedral P4 molecules.