Heterometallic iron calix[n]arenes (n = 6, 8): structure and ring opening polymerization capability.
Sun Qi Q, Wright Victoria E VE, Lee Darren S DS, Motuzis Ignas I et al.
A number of interesting iron-containing calix[n]arene (n = 6, 8) species have been isolated from reactions involving either: in situ-generated heterobimetallic iron alkoxides of the type [MFe(Ot-Bu)3] (M = Na, K) and the parent calixarenes (L6H6 = p-tert-butylcalix[6]areneH6 or L8H8 = p-tert-butylcalix[8]areneH8) or, in the case of LdioxaH6 = p-tert-butyltetrahomodioxacalix[6]areneH6, reaction with [Fe(Ot-Bu)2]. Initial reactions involving the use of L6H6/n-BuLi followed by either FeBr2 or FeBr3 led to the isolation of only lithium-containing calix[6]arene complexes, namely [Li8(L6H2)2(H2O)(MeCN)7]·6.5MeCN (1·6.5MeCN), {[(L6H2)Li6(NCMe)2]2(O)2(H2O)2X2}·14MeCN (2·14MeCN; X = 94%OH, 6%Br). However, the use of L6H6/Na[Fe(Ot-Bu)3] led to the isolation of [Fe3.93Na4.07(L6)(L6H2)(O)(OH)(NCMe)7.75]·5.75MeCN (3·5.75MeCN), whilst for LdioxaH6 following reactions with [Fe(OtBu)2], [Fe(NCMe)2(LdioxaH4)]·3MeCN (4·3MeCN) was isolated. In the case of L8H8, the combination with n-BuLi and subsequently FeCl2 led to [(FeCl)2Fe2(μ3-O)2{Li(NCMe)2}2{Li(NCMe)0.691(THF)0.309}2(L8)(Ot-Bu)2] (5), whereas the use of M[Fe(Ot-Bu)3] (M = Na, K) led to the isolation of {Na[(Fe2O(L8)(Na(NCMe))2)2Fe]}·18MeCN (6·18MeCN), [Fe6O4(L8)(L8H2)Na4(NCMe)5(OH2)(OH)][Fe6O4(L8)(L8H2)Na4(NCMe)4(OH2)2(OH)]·Na(NCMe)4·Na·13MeCN (7·Na(NCMe)4·Na·13MeCN), Fe[(L8H4)K3(NCMe)5]2·8MeCN (8·8MeCN) and [(Fe2K2)(O)(NCMe)5(L8H2)]·5.5MeCN (9·5.5MeCN). The molecular structures of 1-9 were determined. These complexes were screened as catalysts for the ring-opening polymerization (ROP) of the cyclic esters ε-caprolactone (ε-CL) and δ-valerolactone (δ-VL) with and without benzyl alcohol (BnOH). For comparison, the precursors M[Fe(Ot-Bu)3] (M = Na, K) were screened under the same conditions. The results revealed that for the ROP of ε-CL, the catalysts generally performed better under air, with kinetic data revealing the trend 9 > 7 > 6 ≈ 3 > 8 > 4 ≈ 5 ≈ 1 ≈ 2. For δ-VL, conversions across all catalytic systems were much higher, with the rate trend 6 > 9 > 7 > 4 > 3 > 8 > 1 ≈ 5 ≈ 2. MALDI-ToF spectra revealed that different families of products were formed, including linear polymers (with end groups H/OH or H/OBn) and cyclic polymers.