Trinuclear zinc calix[4]arenes: synthesis, structure, and ring opening polymerization studies

The trinuclear zinc calix[4]arene complexes [Zn₃(O₂CCH₃)₂(L(O)₂(OMe)₂)₂·xMeCN (x = 7.5, 1; x = 6, 1′), [Zn₃(O₂CCH₃)₂(L(O)₂(OnPr)₂)₂·5MeCN (2·5MeCN), [Zn₃(OEt)₂(L(O)₂(OMe)₂)₂]·4MeCN (3·4MeCN), [Zn₃(OEt)₂(L(Opentyl)₂)₂]·4.5MeCN (4·4.5MeCN) and [Zn₃(OH)₂(L(O)₂(On-pentyl)₂]·8MeCN (5·8MeCN) have been isolated from reaction of [(ZnEt)₂(L(O)₂(OR)₂)₂] (L(OH)₂(OR)₂ = 1,3-dialkoxy-4-tert-butylcalix[4]arene; R = methyl, n-propyl or pentyl) and the reagents acetic acid, ethanol, and presumed adventitious water, respectively. Attempts to make 5via a controlled hydrolysis led only to the isolation of polymorphs of (L(OH)₂(Opentyl)₂·MeCN. Reaction of [Zn(C₆F₅)₂] with L(OH)₂(Opentyl)₂, in the presence of K₂CO₃, led to the isolation of the complex [Zn₆(L(On-pentyl))₂(OH)₃(C₆F₅)3(NCMe)₃]·3MeCN (6·3MeCN). The molecular structures of 1–6 reveal they all contain a near linear (163 to 179°) Zn₃ motif. In 1–5, a central tetrahedral Zn centre is flanked by trigonal bipyramidal Zn centres, whilst in 6, for the linear Zn₃ unit, a central distorted octahedral zinc centre is flanked by trigonal planar and a tetrahedral zinc centres. Screening for the ring opening polymerization (ROP) of ε-caprolactone at 90 °C revealed that they are active with moderate to good conversion affording low to medium molecular weight products with at least two series of ions. For comparative studies, the trinuclear aminebis(phenolate) complex [Zn₃(Oi-Pr)₂L/] (L/ = n-propylamine-N,N-bis(2-methylene-4,6-di-tert-butylphenolate) I was prepared. Kinetics revealed the rate order I > 4 > 6 ≈ 2 ≈ 1 > 3.