title: Zinc calixarene complexes for the ring opening polymerization of cyclic esters.
abstract: Reaction of Zn(C6F5)2·toluene (two equivalents) with 1,3-dipropoxy-p-tert-butyl-calix[4]arene (L(1)H2) led to the isolation of the complex [{Zn(C6F5)}2L(1)] (1), whilst similar use of Zn(Me)2 resulted in the known complex [{Zn(Me)}2L(1)] (2). Treatment of L(1)H2 with in situ prepared Zn{N(SiMe3)2}2 in refluxing toluene led to the isolation of the compound [(Na)ZnN(SiMe3)2L(1)] (3). The stepwise reaction of L(1)H2 and sodium hydride, followed by ZnCl2 and finally NaN(SiMe3)2 yielded the compound [Zn{N(SiMe3)2}2L(1)] (4). The reaction between three equivalents of Zn(C6F5)2·toluene and oxacalix[3]arene (L(2)H3) at room temperature formed the compound {[Zn(C6F5)]3L(2)} (5); heating of 5 in acetonitrile caused the ring opening of the parent oxacalix[3]arene and rearrangement to afford the complex [(L(2))Zn6(C6F5)(R)(RH)OH]·5MeCN R = C6F5CH2-(p-(t)BuPhenolate-CH2OCH2-)2-p-(t)BuPhenolate-CH2O(-))(3-) (6). The molecular structures of the new complexes 1, 3 and 6, together with that of the known complex 2, whose solid state structure has not previously been reported, have been determined. Compounds 1, 3-5 have been screened for the ring opening polymerization (ROP) of ε-caprolactone (ε-CL) and rac-lactide. Compounds featuring a Zn-C6F5 fragment were found to be poor ROP pre-catalysts as they did not react with benzyl alcohol to form an alkoxide. By contrast, compound 4, which contains a zinc silylamide linkage, was the most active of the zinc-based calix[4]arene compounds screened and was capable of ROP at ambient temperature with 65% conversion over 4 h.
authors.affiliation: Energy Materials Laboratory, School of Chemistry, University of East Anglia, Norwich, NR4 7TJ, UK.
authors.forename: Mark J
authors.initials: MJ
authors.lastname: Walton
authors.forename: Simon J
authors.initials: SJ
authors.lastname: Lancaster
authors.forename: Joseph A
authors.initials: JA
authors.lastname: Wright
authors.forename: Mark R J
authors.initials: MR
authors.lastname: Elsegood
authors.forename: Carl
authors.initials: C
authors.lastname: Redshaw