Synthesis and characterisation of lanthanide phenolate compounds and their catalytic activity towards ring-opening...

Five new heteroleptic lanthanide(III) phenolate compounds have been synthesised in high yield, four via a transamination reaction between Ln(N(SiMe(3))2)3 and two equivalents of the phenol, HOC(6)H(2)(2,4-Bu(t))-6-CH(2)N(Me)CH(2)CH(2)NMe(2) [corrected] (LH) in thf {L(2)LnN(SiMe(3))2 where Ln = La (1); Nd (2); Sm (3); Yb (4)}. The fifth compound, [L(2)La][BPh(4)] 5 was formed by conversion of 1 by treatment with one equivalent of [Et(3)NH][BPh(4)] in toluene. Compound 3 was subjected to a single-crystal X-ray analysis and revealed a five-coordinate, distorted trigonal bipyramidal samarium(III) metal centre where each phenolate ligand is bidentate coordinating through the phenolate oxygen and nitrogen yielding six-membered chelate rings. Compound 1 exhibited fluxional behaviour in C(4)D(8)O solution which was temperature dependent. All five compounds were assessed as catalyst precursors towards the ring-opening polymerisation of both L-lactide and epsilon-caprolactone. These polymerisation studies revealed that catalysts containing larger lanthanide metals were more efficacious than those with smaller lanthanide metals. Furthermore, replacement of the [N(SiMe(3))2] initiating group in 1 with [BPh(4)] in 5 reduced catalytic activity by this compound. Detailed kinetics analysis of the ring-opening polymerisation of L-lactide by compound 1, the most efficacious catalyst precursor analysed in this study, revealed the following rate law: -d[LA]/dt = k[LA](2)[1](1) which is second order in lactide and first order in catalyst. End-group analysis by ESI mass spectrometry revealed the presence of phenolate end-groups and lactide cycles, the latter formed by intra-molecular, intrachain transesterification.