Heteroleptic tethered NHC rare earth initiators for the ring opening polymerisation of <i>rac</i>-lactide

The importance of catalyst design is shown by the contrasting reactivity of tethered NHC and Tp ligands with rare-earth metal centres highlighting that successful catalyst design is not as simple as linearly combining moieties with known catalytic activity. The heteroleptic fluorenyl-tethered-NHC rare-earth complexes LnLX₂ [Ln = Y, La, Ce, Nd; L = (η⁵-C₁₃H₈)C₂H₄N(κ-C)C₂H₂NMe; X = N'' or Br] were synthesised from [Ln{N(SiMe₃)₂}₃] (LnN''₃), with X selected by varying the precursor. Direct addition of LnN''₃ to the fluorene-tethered imidazolium salt LH₂Br proceeded with loss of two equivalents of HN(SiMe₃)₂ forming [LnL(N'')Br] complexes; alternatively, initial deprotonation of LH₂Br with ^<i>n</i>BuLi or KCH₂Ph prior to addition of LnN''₃ yielded [LnL(N'')₂] complexes. [LnL(N'')Br] [Ln = Ce (3), Nd (4)] are dimeric through bridging Br ligands whereas [LnL(N'')₂] [Ln = La (5), Ce (6), Nd (7)] are monomeric. These complexes were investigated for their activity and selectivity in the ring opening polymerization (ROP) of <i>rac</i>-lactide using benzyl alcohol as a co-initiator, showing high activity with full conversion typically being obtained in under 15 minutes at room temperature. Comparisons with the yttrium amide complex [Y(Tp)₂(N'')] (8, Tp = hydrotris(1-pyrazolyl)borate) demonstrated the important role of the fluorenyl-tethered NHC ligand in generating an active catalyst, illustrating that simply having a rare-earth metal centre with a bis(trimethylsilyl)amide group is not enough to generate an effective (pre)catalyst. Finally, we hope to raise awareness that a trace impurity of lactic acid, sometimes present in commercial <i>rac</i>-lactide, greatly inhibited ROP and was not easily removed by sublimation or re-crystallisation.