Titanium complexes bearing oxa- and azacalix[4, 6]arenes: structural studies and use in the ring opening homo-/co-polymerization of cyclic esters

Abstract

Reaction of excess [Ti(OiPr)₄] with p-tert-butyltetrahomodioxacalix[6]areneH₆ (L¹H₆) afforded, after work-up (MeCN), the complex [Ti₂(OiPr)₂(MeCN)L¹]·3.5MeCN (1·3.5MeCN), whilst the oxo complex [Ti₄(μ₃-O)₂(H₂O)(L¹)₂]·MeCN (2·MeCN) was isolated via a fortuitous synthesis involving the use of two equivalents of [Ti(OiPr)₄]. Reactions of p-methyl-dimethyldiazacalix[6]areneH₆ (L²H₆) with [TiF₄] (four equivalents), [TiCl₄(THF)₂] (two equivalents) or [TiBr₄] (>four equivalents) resulted in the titanium-based azacalix[n]arene complexes [Ti₄F₁₄L²H₂(H)₂]·2.5MeCN (3·2.5MeCN), [Ti₂X₄(H₂O)₂OL²H₂(H)₂] (X = Cl (4·5MeCN), Br (5·4.5MeCN) and [Ti₄Br₁₂L²(H)₂(MeCN)₆]·7MeCN (6·7MeCN), respectively. Reaction of four equivalents of [TiF₄] with L³H₄ (L³H₄ = p-methyl-dimethyldiazacalix[4]areneH₄) afforded the product [Ti₂F₂(μ-F)₃L³(H)₂(SiF₅)]·2MeCN (7·2MeCN). These complexes have been screened for their potential to act as pre-catalysts in the ring opening polymerization (ROP) of ε-caprolactone (ε-CL), δ-valerolactone (δ-VL) and rac-lactide (r-LA). Generally, the titanium complexes bearing oxacalixarene exhibited better activities than the azacalixarene-based pre-catalysts. For ε-CL, δ-VL and r-LA, moderate activity at 130 °C over 24 h was observed for 1–6. In the case of the co-polymerization of ε-CL with r-LA, 1–6 afforded reasonable conversions and high molecular weight polymers; 7 exhibited lower catalytic performance due to low solubility. None of the complexes proved to be active in the polymerization of ω-pentadecalactone (ω-PDL) under the conditions employed herein.