Lead calix[n]arenes (n = 4, 6, 8): structures and ring opening homo-/co-polymerization capability for cyclic esters

Abstract

Reaction of [LiPb(OiPr)₃]₂ (generated in situ) with either p-tert-butylcalix[4]areneH₄ (L⁴H₄) or p-tert-butylcalix[6]areneH₆ (L⁶H₆) resulted in the heterometallic lithium/lead complexes [Pb₄Li₂(L⁴)₄H₆(MeCN)₃]·4.5MeCN (1·4.5MeCN) and [Pb₈Li₁₀Cl₂(L⁶H₂)₃(L⁶)(OH)₂(O)₂(H₂O)₂(MeCN)₄]·14MeCN (2·14MeCN), respectively. Use of the dimethyleneoxa-bridged p-tert-butyltetrahomodioxacalix[6]areneH₆ (L^6′H₆) with five equivalents of [Pb(OiPr)₂] afforded [Pb₁₃(L^6′)₃O₄(iPrOH)]·11MeCN (3·11MeCN). Use of the larger p-tert-butylcalix[8]areneH₈ (L⁸H₈) with [Pb(OtBu)₂] or {Pb[N(TMS)₂]} (TMS = SiMe₃) afforded the products [Pb₁₂(L⁸)₂O₄]·8.7C₇H₈ (4·8.7C₇H₈) or [Pb₆(SiMe₃)₂(L⁸)O₂Cl₂] (5), respectively. Reaction of {Pb[N(TMS)₂]} (generated in situ from (Me₃Si)₂NH, nBuLi and PbCl₂) with L⁶H₆ afforded, after work-up (MeCN), the mixed-metal complex [Pb₁₀Li₂(L⁶)₂(OH)Cl(O)₄]·9.5MeCN (6·9.5MeCN). Reaction of distilled {Pb[N(TMS)₂]} (six equivalents) with L⁸H₈ resulted in the complex [Pb₁₂(L⁸)₂O₄]·12MeCN (7·12MeCN). Complexes 1–7, Pb(OiPr)₂ and [Pb(N(TMS)₂)₂] have been screened for their potential to act as pre-catalysts in the ring opening polymerization (ROP) of ε-caprolactone (ε-CL) and δ-valerolactone (δ-VL) and the copolymerization thereof. Generally, the lithiated complexes 1 and 2 exhibited better activities than the other pre-catalysts screened herein. For ε-CL and δ-VL, moderate activity at 130 °C over 24 h was observed for 1–7. In the case of the co-polymerization of ε-CL with δ-VL, 1–7, Pb(OiPr)₂ and [Pb(N(TMS)₂)₂] afforded reasonable conversions and high molecular weight polymers. The systems 1–7, Pb(OiPr)₂ and [Pb(N(TMS)₂)₂] also proved to be active in the ROP of the rac-lactide (r-LA); the activity trend was found to be 1 > 2 ≈ Pb(OiPr)₂ ≈ [Pb(N(TMS)₂)₂] > 4 > 5 ≈ 6 ≈ 7 > 3.