Interaction Modes of Titanium Tetrachloride with the Carbonyl Functionality

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Abstract
Mesityl aldehyde binds TiCl4 leading to the first structurally characterized TiCl4‐aldehyde adduct, cis‐[(MesCHO)2TiCl4] (Mes = 2,4,6‐Me3C6H2) (1), which contains a pseudooctahedral titanium and two aldehyde carbonyl groups in a cis arrangement. However, in the case of 1:1 TiCl4–acetone adduct [(Me2CO)TiCl3)2(μ‐Cl)2] (3) the solid‐state structure of this acid‐base complex is that of a chloro‐bridged dimer. Both kinds of structures were suggested for the products [{(PhCOMe)TiCl3}2(μ‐Cl)2] (4) and [cis‐(PhCOMe)2TiCl4] (5) formed by the reaction of TiCl4 with acetophenone in 1:1 and 1:2 molar ratio. Thioesters behave like acetone in that they give adducts 8 and 9 with TiCl4, where 9, [{(PhSC(Me)O)TiCl3}2(μ‐Cl)2], exhibits a solid‐state dimeric structure like 3. The bidentate bonding mode of the chiral propionyloxazolidone 12 with TiCl4 was revealed by an X‐ray analysis of 13.

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