DONOR-STABILIZED OXIDE AND OXIDE FLUORIDE OF MAIN GROUPS ELEMENTS Z. Zák, M. Éerník, K. Neplechová, J. Touzin, Department of Inorganic Chemistry, Masaryk University, Brno, Czech Rebublic.
The crystal structures of two new compounds,[F2OP-O-PF2(bipy)-O-POF2]+[PO2F2]- (I), and [O3Se-O-SeO(py)3].py (II), with different coordination numbers of P or Se atoms were determined. The middle P atom in (I) is surrounded by six ligands in a nearly octahedral configuration, while terminal P atoms are coordinated tetrahedrally. The cation of (I) which can be formally derived from PF4+ cation [1] by coordination of one molecule of 2,2'-bipyridine and a substitution of two F atoms by -OP(O)F2 groups has both F atoms in cis-positions and represents the first reported halogenophosphorus(V) cation with more than one P atom in the molecule. The compound (II) can be regarded as monomeric diselenium pentaoxide stabilized by coordination of pyridine. While crystalline Se2O5 is a coordination polymer forming infinite zig-zag chains of oxygen-bridged Se(IV)O and Se(VI)O2 units [2], (II) represents rather a covalent seleninyl selenate. The Se(IV) atom of the seleninyl group is coordinated by one O atom of the selenate and three pyridine molecules in a [[psi]]-octahedral fashion.
References:
[1] Chen G.S.H., Passmore J.: J. Chem. Soc. (Dalton) 1979, 1251. [2] ZakZ.: Z. anorg. allg. Chem. 460, 81 (1980).