Issue 3, 2024

Flexible NHC-aryloxido aluminum complex and its zwitterionic imidazolium aluminate precursor in ring-opening polymerization of ε-caprolactone

Abstract

Anionic donor-functionalized NHC (N-heterocyclic carbene) complexes of Al are rare. We report one such case here, an NHC-aryloxido AlMe2 complex [Al(L)Me2] (2), following a stepwise synthesis from the proligand [HO-4,6-tBu2-C6H2-2-CH2{CH(NCH[double bond, length as m-dash]CHNAr)}]Br [LH2Br; Ar = 2,6-iPr2-C6H3 (Dipp)] and AlMe3via the zwitterionic intermediate [Al(LH)Me2Br] (1). The ligand's flexibility in 2 is evident from the conformational fluxionality revealed by VT-1H NMR spectroscopic analysis. The ∠O–Al–C (ca. 100.5°) bite angle is also wider than the ∠O–Ti–C (ca. 80.6°) as seen in our recently reported Ti complex [Ti(L)(NMe2)2Br]. DFT analysis showed that the CNHC–Al bond is significantly ionic, as is the CNHC–Ti bond. Both 1 and 2 are active in the ring-opening polymerization (ROP) of ε-caprolactone (CL). 2, similar to [Ti(L)(NMe2)2Br], exhibits bifunctional MLC-type monomer activation, but only at an elevated temperature. However, the 2/BnOH combination is catalytically active at room temperature, likely through a zwitterionic [Al(LH)Me2(OBn)]. The 1/BnOH combination follows a similar mechanism but surprisingly at a faster rate.

Graphical abstract: Flexible NHC-aryloxido aluminum complex and its zwitterionic imidazolium aluminate precursor in ring-opening polymerization of ε-caprolactone

Supplementary files

Article information

Article type
Paper
Submitted
08 сен 2023
Accepted
08 дек 2023
First published
11 дек 2023

Dalton Trans., 2024,53, 1346-1354

Flexible NHC-aryloxido aluminum complex and its zwitterionic imidazolium aluminate precursor in ring-opening polymerization of ε-caprolactone

S. Goswami, P. Mandal, S. Sarkar, M. Mukherjee, S. Pal, D. Mallick and D. Mukherjee, Dalton Trans., 2024, 53, 1346 DOI: 10.1039/D3DT02932H

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