Synthesis and structures of mono- A nd di-nuclear aluminium and zinc complexes bearing α-diimine and related ligands, and their use in the ring opening polymerization of cyclic esters

A series of organoaluminium imino-amido complexes of the type {[ArNC(Me2)C(Me)NAr]AlMe2} (Ar = 2,6-iPr2C6H3 (1), Ar = 2,6-Et2C6H3 (2); Ar = 2,6-Me2C6H3 (3) have been prepared via reaction of AlR3 and the respective α-diimine. Similar reaction of the bis(α-diimine) [ArNC(Me)C(Me)N-]2 (Ar = 2,6-iPr2C6H3) with AlMe3 afforded the bimetallic complex [ArN-C(Me)2C(Me)NAlMe2]2 (4), whilst reaction of the acetyl-imino compound [OC(Me)C(Me)NAr] (Ar = 2,6-Et2C6H3) with AlMe3 afforded the bimetallic complex {[OCMe2CH(Me)NAr]AlMe2}2 (5). In related organozinc chemistry, we have isolated {[ArNC(Me)(Et)C(Me)NAr]ZnEt} (Ar = 2,6-iPr2C6H3, 6) and the trinuclear complex {[ArNC(Me)COCHCO(Me)C(Me)NAr][OCH(Me)C(Me)NAr](ZnEt)3} (Ar = 2,6-iPr2C6H3, 7) from reactions of ZnEt2 with ArNC(Me)C(Me)NAr or [OC(Me)C(Me)NAr], respectively. Reaction of the bis(α-diimine), LiPr-Njavax.xml.bind.JAXBElement@4341536-ArCHjavax.xml.bind.JAXBElement@34edcd12Ar-Njavax.xml.bind.JAXBElement@3b4b2289, derived from 4,4′-methylenebis(2,6-diisopropylaniline), with ZnCl2 affords [LiPr-Njavax.xml.bind.JAXBElement@5bf257fb-ArCHjavax.xml.bind.JAXBElement@7fcb6416Ar-Njavax.xml.bind.JAXBElement@2594a3a0(ZnCl2)2] (8). The molecular structures of complexes 1-8 are reported. Preliminary results of the ability of 1-8, along with the previously reported metal-metal bonded complex {[ArNC(Me)C(Me)NAr]Al(THF)}2 (9), to act as catalysts for the ring opening polymerization (ROP) of the cyclic esters ϵ-caprolactone (ϵ-CL), δ-valerolactone (δ-VL) and rac-lactide (r-LA) are presented. For ϵ-CL and δ-VL, best results were obtained using the metal-metal bonded complex 9. For r-LA, the Al-based systems exhibited moderate activity affording only liquid oligomers, whilst the Zn-based systems performed better affording at 80 °C isotactic PLA with Mnca. 10 kDa with conversions of up to 66%. The co-polymerization of ϵ-CL with δ-VL was also examined, and differing preferences were noted for monomer incorporation.