In the present work the bonding situation within the P4O6X2 (X = O, S and Se) series is analysed by means of the geometrical structures and the IR spectra of those molecules. The experimental data are obtained from pure P4O8 and P4O6Se2 crystals which could be synthesized for the first time. The theoretical geometrical structures were obtained by employing the Hartree-Fock method in combination with a basis set of double zeta quality plus polarization functions. Theoretical vibrational spectra calculated with the same method were refined by using the Scaled Quantum Mechanical method proposed by Pulay. Our study shows that the doubly substituted compounds behave very similar to the monosubstituted molecules, e. g. shifts of the vibrational frequencies result mainly from the differences in the bond strengths of the P = X units and the different masses of the substituents, while the bonding situation within the P4O6 frame remains nearly unchanged within this series.

Abstract P4O8 was synthesized for the first time in a pure state. Its crystal structure has been refined using X-ray diffractometer data (monoclinic, C2/c with a = 970.0(2); b = 1017.9(2); c = 692.3(1) pm; β = 96.95(2)°; V = 678.5 Å3; R1 = 0.033; wR2 = 0.073). Molecular geometry and packing in the solid state are discussed.

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Reaction of tetraphosphorus hexaoxide with organic azides leads selectively to the cage redistribution products 1 P(4)O(6)NPh, 2 P(4)O(6)NC(2)H(4)Ph, 3 P4O6NSO2CH3, 4 P4O6NC6H13, and 5 P4O6NCO2C2H5 nitrene insertion. The molecular structure consists of an adamantane-like P4O5N cage with a terminally bound oxygen The P4O5N cagelike structure is confirmed by P-31 NMR spectroscopy and X-ray structure analysis. The P4O5N cages of the P(4)O(6)NR molecules possess a significant geometrical distortion.

P4O7S was synthesized for the first time and characterized by X-ray structure determination (single-crystal methods) and P-31-n.m.r. (solution and MAS-solid) (P $($) over bar$$ 1; a = 687.2(1); b = 718.2(1); c = 809.1(1) pm; alpha = 92.58(1)degrees; beta = 104.43(1)degrees; gamma = 94.82(2)degrees; 2907 diffractometer data; R(1) = 0.030; wR(2) = 0.102). The different influences of terminally bound oxygen and sulfur on the geometry of the P4O6 cage are discussed.

Preparation and crystal structure of [P(C6H5)(4)]Cl-3 are reported. [P(C6H5)(4)]Cl-3 crystallizes in the monoclinic space group P2(1)/c with a = 1093.4(4), b = 789.1(1), c = 2682.7(7) pm, beta = 90.39(1)degrees, V = 2200.27 10(6) pm(3), and Z = 4. The geometry of the trichloride anion in the solid state is almost linear (Cl-Cl-Cl = 178.44(4)degrees) and unsymmetrical (d(Cl-Cl) = 226.3(1) and 230.7(1) pm).

P4 O6 NR (R =–Ph, –C2H4Ph, –n-C6H13, –SO2Me, –CO2Et) are obtained from the reaction of tetraphosphorus hexaoxide with organic azides; the P4O5N cage-like structure is confirmed by 31P NMR spectroscopy and X-ray structure analysis of P4O6NC6H5.

Preparation and crystal structure of [P(C6H5)4]Cl3 are reported. [P(C6H5)4]Cl3 crystallizes in the monoclinic space group P21/c with a = 1093.4(4), b = 789.1(1), c = 2682.7(7) pm, β = 90.39(1)°, V = 2200.27·106 pm3, and Z = 4. The geometry of the trichloride anion in the solid state is almost linear (Cl-Cl-Cl = 178.44(4)°) and unsymmetrical (d(Cl-Cl) = 226.3(1) and 230.7(1) pm).