Edge-Shared [M2Cl10]2- Complexes of Reaction between Oxophilic Group IV Metal and Phosphorus Ylides

Abstract

The reactions between oxophilic group 4 metal chlorides, a-keto ylides in THF, led to the formation of titanium, zirconium and hafnium edge-shared [M₂Cl₁₀]^2- complexes (1a-3d). With adding dimethyl sulfoxide as a ligand to these complexes at room temperature crystalline solid [M(DMSO)₈]·4Cl·mH₂O·DMSO] (M = Ti (1g), Zr (2g) and Hf (3g); m = 0-3) together with phosphonium salts in mother liquid were formed. Its metal complexes have been characterized by elemental analysis, IR and ¹H, ¹³C and ³¹P NMR spectroscopy. The dominating coordination structures of 1g-3g are seven-coordinated complexes.