Metal Complexes in Inorganic Matrixes. 18.1 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 [Ph 2 PCH 2 CH 2 COO]EO x (OR) 3 - 2 x (E = Ti, Zr) were obtained by two routes: by HPPh 2 addition to the double bond of [CH 2 CHCOO]EO x ‘ (OR) 3 - 2 x ‘ and by reaction of E(OR) 4 with Ph 2 PCH 2 CH 2 COOH. The second route results in less byproducts. The sulfonate derivatives [Ph 2 PCH 2 CH 2 SO 3 ]EO x (OR) 3 - 2 x and the hydroxamate derivatives [Ph 2 PCH 2 CH 2 ClO)N(H)O]EO x (OR) 3 - 2 x were prepared by the second route, i.e., reaction of Na[O 3 SCH 2 CH 2 PPh 2 ] or K[ON(H)C(O)CH 2 CH 2 PPh 2 ] with E(OR) 4 . Reaction of (CO) 5 W(OEt 2 ) with the compounds Ph 2 P−X−E(OR) 3 gave the phosphine complexes W(CO) 5 [PPh 2 −X−E(OR) 3 ] in each case. The bond between the titanium or zirconium atom and the PPh 2 -substituted bidentate ligand is hydrolytically stable. The X-ray structure analysis of Zr(OPr)(O 3 SMe) 3 showed the compound to have a chain structure with two bridging and one chelating sulfonate group per zirconium atom.