Organodioxygen complexes of some group 4B metal ions

Organodioxygen complexes of some group 4B metal ions, viz., zirconium(IV), tin(IV) and lead(II) containing monodentate, bidentate and tridentate ligands were synthesized and characterized. The complexes have the compositions of [Zr(O)(O2)2C5H5N.H2O], [Zr(O)(O2-)2.2OPPh3], [Sn(O2)(C9H6NO)2], [Sn(02)2.(CH2)2(NH2)2], [Pb(O2-)(C5H5N)2NO3], [Pb(O2)(C8H6NOH)], [Pb(O2-)(det)NO3] and [PbO2-) (C5H4NCOOH)NO3.H2O]. Because of apparent linearity of M- O2 grouping, the V1(O-O) stretching modes were only Raman active, giving bands at 810- 841 cm1 for the peroxo complexes (1, 3, ,4 and 6), while the bands in the superoxo complexes (2, 5, 7 and 8) appeared at 1020- 1100 cm-1. The peroxo complex of Zr(IV) containing monodentate ligands were found to oxidize trans-stilbene to trans-stilbene oxide under stoichiometric conditions. The organoperoxo complexes of tin and lead were insensitive to oxidative processes. (author)