Lithium calix[4]arenes: structural studies and use in the ring opening polymerization of cyclic esters

We have structurally characterized a number of lithiated calix[4]arenes, where the bridge in the calix[4]arene is thia (-S-, LSH4), sulfinyl (-SO-, LSOH4), sulfonyl (-SO2-, LSO2H4), dimethyleneoxa (-CH2OCH2-, LCOCH4) or methylene (-CH2-, LH4). In the case of L4SH4, interaction with LiOtBu led to the isolation of the complex [Li8(L4S)2(THF)4]·5THF (1·5THF), whilst similar interaction of L4SOH4led to the isolation of [Li6(L4SOH)2(THF)2]·5(THF) (2·5THF). Interestingly, the mixed sulfinyl/sulfonyl complexes [Li8(calix[4]arene(SO)(SO2)(SO1.68)2)2(THF)6]·8(THF) (3·8THF) and [Li5Na(LSO/3SO2H)2(THF)5]·7.5(THF) (4·7.5(THF) have also been characterized. Interaction of LiOtBu with LSO2H4and LCOCH4afforded [Li5L4SO2(OH)(THF)4]·2THF (5·2THF) and [Li6(LCOC)2(HOtBu)2]·0.78THF·1.22hexane (6·0.78THF·1.22hexane), respectively. In the case of LH4, reaction with LiOtBu in THF afforded a monoclinic polymorph [LH2Li2(thf)(OH2)2]·3THF (7·3THF) of a known triclinic form of the complex, whilst reaction of the de-butylated analogue of LH4, namely de-BuLH4, afforded a polymeric chain structure {[Li5(de-BuL)(OH)(NCMe)3]·2MeCN}n(8·2MeCN). For comparative catalytic studies, the complex [Li6(LPr)2(H2O)2]·hexane (9hexane), where LPr2H2= 1,3-di-n-propyloxycalix[4]areneH2, was also prepared. The molecular crystal structures of1-9are reported, and their ability to act as catalysts for the ring opening (co-)/polymerization (ROP) of the cyclic esters ε-caprolactone, δ-valerolactone, andrac-lactide has been investigated. In most of the cases, complex6outperformed the other systems, allowing for higher conversions and/or greated polymerMn