Mono(aryloxido)Titanium(IV) Complexes and Their Application in the Selective Dimerization of Ethylene

We report on the synthesis of mono(aryloxido)titanium(IV) complexes of general formula {Ti[O(o‐R)Ar]X3}, with X = OiPr, ArO = 2‐tert‐butyl‐4‐methylphenoxy and R = CMe3 (2a), CMe2Ph (2b) and CH2NMe2 (2c). Attempts to reach pure mono(aryloxido) complexes when R = CH2NMe(CH2Ph) (2d) or CH2N(CH2Ph)2 (2e) were unsuccessful. When R = CH2OMe, the analogous mononuclear complex was not obtained, and instead, a dinuclear complex [(2‐tert‐butyl‐4‐methyl‐6‐methoxymethylphenoxy) TiCl(OiPr)(μ2‐OiPr)2TiCl(OiPr)2] (3) was formed. Complexes 2b and 3 were characterized by single‐crystal X‐ray diffraction. The former contains a tetrahedrally coordinated TiIV centre, whereas in the latter the aryloxido ligand behaves as a chelating–bridging ligand between the two, chemically very different metal centres that form two face‐sharing octahedra. Different synthetic approaches starting from [Ti(OiPr)4] or [TiCl(OiPr)3] were evaluated and are discussed. The hemilabile behaviour of the aryloxido ligand resulting from reversible coordination of its side arm was studied by variable‐temperature 1H NMR spectroscopy for 2c (R = CH2NMe2). Complexes 2a–d were contacted with ethylene and AlEt3 as cocatalyst. When activated with AlEt3 (3 equiv.) at 20 bar and 60 °C, complex 2c exhibits interesting activity (2100 g/gTi/h) for the selective dimerization of ethylene to 1‐butene (92 % C4=; 99+% C4=1). Noticeable differences in catalyst activity were observed when the R group was modified. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009)