Metal complexes in inorganic matrixes .18. Phosphanyl-substituted titanium and zirconium alkoxides for tethering metal complexes on titania or zirconia and the X-ray structure analysis of polymeric Zr(OPr)(O3SMe)(3)

The compounds [Ph2PCH2CH2COO]EOx(OR)(3-2x) (E = Ti, Zr) were obtained by two routes: by HPPh2 addition to the double bond of [CH2=CHCOO]EOx'(OR)(3-2x') and by reaction bf E(OR)(4) with Ph2PCH2CH2COOH. The second route results in less byproducts. The sulfonate derivatives [Ph2PCH2CH2SO3]EOx(OR)(3-2x) and the hydroxamate derivatives [Ph2PCH2CH2ClO)N(H)O]EOx(OR)(3-2x) were prepared by the second route, i.e., reaction of Na[O3SCH2CH2PPh2] or K[ON(H)C(O)CH2CH2PPh2] with E(OR)(4). Reaction of (CO)(5)W(OEt2) with the compounds Ph2P-X-E(OR)(3) gave the phosphine complexes W(CO)(5)[PPh2-X-E(OR)(3)] in each case. The bond between the titanium or zirconium atom and the PPh2-substituted bidentate ligand is hydrolytically stable. The X-ray structure analysis Of Zr(OPr)(O3SMe)(3) showed the compound to have a chain structure with two bridging and one chelating Sulfonate group per zirconium atom.