Group 4 Organometallics Supported by Sterically Hindered β‐Diketonates

Abstract

The synthesis, characterization, and reactivity of group 4 organometallics supported by -diketonates is reported. Sterically hindered -diketonates, such as 2,6-dimesitylbenzoyl pinacolone (L 1 ) and 2,6-dimesitylbenzoyl acetylmesitylene (L 2 ), preclude the formation of tetrakis-and tris-chelates, halting at cis-octahedrally coordinated M(L n ) 2 Cl 2 (M = Ti, Zr, Hf; L n = L 1 , L 2 ). Metathesis with benzylmagnesium chloride affords M(L n ) 2 Bn 2 (M = Zr, Hf ) and the reduced Ti(L 1 ) 2 Bn(THF) species. These are the first structurally-characterized metal alkyl complexes exclusively supported by -diketonates among the [a] E.Figure 2. Crystal structures of the group 4 organometallics. Thermal ellipsoids (50 % confidence level) are drawn for the chelate rings and benzyl substituents.