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Journal Article

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


van Wüllen,  L.
Abteilung Jansen, Former Departments, Max Planck Institute for Solid State Research, Max Planck Society;

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Krossing, I., & van Wüllen, L. (2002). Superweak complexes of tetrahedral P4 molecules with the silver cation of weakly coordinating anions. Chemistry - A European Journal, 8(3), 700-711.

Cite as: https://hdl.handle.net/21.11116/0000-000E-E2B7-4
The silver aluminates AgAl[OC(CF3)(2)(R)](4) (R = H, CH3, CF3)
react with solutions of white phosphorus P-4 to give complexes
that bind one or two almost undistorted tetrahedral P-4
molecules in an eta(2) fashion: [Ag(P-
4)(2)](+)[Al(OC(CF3)(3))(4)](-) (1) containing the first
homoleptic metal-phosphorus cation, the molecular species (P-
4)AgAl[OC(CH3)(CF3)(2)](4) (2), and the dimeric Ag(mu,eta(2)-P-
4)Ag bridged {(P-4)AgAl[OC(CH3)(CF3)(2)]4}(2) (3). Compounds 1-
3 were characterized by variable-temperature (VT) P-31 NMR
spectroscopy (1 also by VT P-31 MAS-NMR spectroscopy), Raman
spectroscopy, and single-crystal X-ray crystallography. Other
Ag:P-4 ratios did not lead to new species, and this observation
was rationalized on thermodynamic grounds. The Ag(P-4)(2)(+)
ion has an almost planar coordination environment around the
Ag+ ion due to d(x2-y2)(Ag) --> sigma*(P-P) back-bonding.
Calculations (HF-DFT) on six Ag(P-4)(2)(-) isomers 4a-f showed
that the planar eta(2) form 4a is only slightly favored by 5.2
kJ mol(-1) over the tetrahedral eta(2) species 4b: eta(1)-P-4
and eta(3)-P-4 complexes are less favorable (27 - 76 kJ mol(-
1)). The bonding of the P-4 moiety in [RhCl-(eta(2) -P-
4)(PPh3)(2)], the only compound in which an eta(2) bonding mode
of a tetrahedral P-4 molecule has been claimed, must be
regarded as a tetraphosphabicyclobutane, and not as a
tetrahedro-P-4 complex, on the basis of the published NMR and
vibrational spectra, the calculated geometry of [RhCl(P-
4)(PH3)(2)] (10), the highly endothermic (385 kJ mol(-1))
calculated dissociation enthalpy of 10 into P-4 and
RhCl(PH3)(2) (11), as well as atoms in molecules (AIM) and
natural bond orbital (NBO) population analyses of 10 and the
Ag(P-4)(2)(+) ion. Therefore, 1-3 are the first examples of
species containing eta(2)-coordinated tetrahedral P-4