Mono- and Bimetallic Aluminum Complexes Supported by Thioether-Amide Ligands: Synthesis, Characterization, and Application in the Ring Opening Polymerization of l-Lactide

Abstract

Mono-and bimetallic aluminum complexes bearing bidentate NS or tetradentate NSSN ligands have been synthesized via reaction of AlMe 3 with the corresponding proligand and spectroscopically characterized. In these complexes the aluminum centers are surrounded by anionic nitrogen and neutral sulfur atoms that, together with the carbon atoms of the alkyl groups, produce tetrahedral coordination geometries. In the bimetallic complexes the two metal centers are linked by a thioether-bridge of different lengths. The solid state structure of the complexes featuring the thioethyl or thiopropyl bridge were determined by X-ray diffraction studies. Both mono-and bimetallic aluminum complexes display fluxional behaviors in solution. After proper activation, all complexes were able to promote the ring opening polymerization of L-lactide in toluene solution. The polymerizations were well controlled as testified by the linear increase of the molecular weights with the conversions and the narrow polydispersity indexes. The highest activity was observed for the bimetallic complex bearing the NSSN ligand with the shortest bridge (ethyl bridge) with a turnover frequency of 11.6 mol LA •mol Al −1 •h −1 (toluene, 80 °C). The activity decreased as the distance between the two metal centers increased. Moreover, the activity of the bimetallic complex with the ethyl bridge was higher than those of the monometallic ones. These findings suggest that a cooperative interaction between two aluminum centers is operative in the bimetallic complex with the shortest bridge.

Aluminum complexes of a hemilabile pyrrolylaldiminate ligand

“…Aluminum complexes containing formally anionic N-donor ligands have received considerable attention because of their essential roles in Lewis acid catalysis [1][2][3][4][5] and polymerization chemistry [6][7][8][9][10]. Chelating ligands investigated in this regard (Figure 1a) include bidentate [N^N] À [11][12][13][14][15][16][17][18][19][20][21], [N^O] À [21][22][23][24], [N^S] À [25],…”

“…H NMR (C 6 D 6 , 500 MHz) δ 7.16 (s, 1, CH N),6.75 (d, 1, 3 J HH = 3.5, pyrrolyl-CH), 6.39 (d, 1, 3 J HH = 3.5, pyrrolyl-CH), 2.91 (t, 2, CH 2 ), 2.09 (t, 2, CH 2 ), 1.94 (s, 6, NMe 2 ), 1.44 (s, 9, CMe 3 ), À0.30 (s, 6, AlMe 2 ) 13. C NMR (C 6 D 6 , 125 MHz) δ 161.83 (pyrrolyl-C), 159.36 (CH N), 134.87 (pyrrolyl-C), 120.64 (pyrrolyl-CH), 111.77 (pyrrolyl-CH), 58.99 (CH 2 ), 50.46 (CH 2 ), 45.66 (NMe 2 ), 34.10 (CMe 3 ), 31.82 (CMe 3 ), À7.68 (Δv 1/2 = 37.5, AlMe 2 ).…”

Ring-Opening Polymerization of rac-β-Butyrolactone Promoted by New Tetradentate Thioether-Amide Ligand-Type Zinc Complexes

“…As part of our research interests [21][22][23][24], we have developed a series of group 4 and aluminum metal complexes featuring tetradentate thioether-amide ligands (NSSNs) and studied their activity in the ROP of cyclic esters [25][26][27]. Since these ligands present an intriguing combination of hard and soft donor groups, we thought that they could match the "borderline" soft Lewis acid character of zinc ions, influencing their reactivity positively.…”