Dialkylaluminium 2-imidazolylphenolates: Synthesis, characterization and ring-opening polymerization behavior towards lactides

The stoichiometric reaction of the 2-imidazolylphenols (L1–L9) with the trialkylaluminium reagents AlR₃ (R = Me, Et and iBu), afforded the corresponding dialkylaluminium 2-imidazolylphenolate complexes [R₂Al(L1–L9)] (C1–C11), which were characterized by ¹H/¹³C NMR spectroscopy and by elemental analysis. The molecular structures of the representative complexes C1, C2, C4, C6 and C11 were determined by single-crystal X-Ray diffraction, and revealed a distorted tetrahedral geometry at aluminum. These dialkylaluminium 2-imidazolylphenolates (C1–C11) could efficiently catalyze the ring-opening polymerization of lactides to afford high molecular weight polylactide, both in the presence and absence of BnOH, and as such represent rare examples of the use of bi-dentate ligation at aluminum in such lactide polymerization systems. On the basis of the polymerization results for l-lactide, d-lactide and rac-lactide, the nature of the ligands and the aluminum bound alkyls were found to significantly affect the catalytic activity as well as the properties of the resultant polylactides

Zinc calixarene complexes for the ring opening polymerization of cyclic esters

Reaction of Zn(C₆F₅)₂·toluene (two equivalents) with 1,3-dipropoxy-p-tert-butyl-calix[4]arene (L¹H₂) led to the isolation of the complex [{Zn(C₆F₅)}₂L¹] (1), whilst similar use of Zn(Me)₂ resulted in the known complex [{Zn(Me)}₂L¹] (2). Treatment of L¹H₂ with in situ prepared Zn{N(SiMe₃)₂}₂ in refluxing toluene led to the isolation of the compound [(Na)ZnN(SiMe₃)₂L¹] (3). The stepwise reaction of L¹H₂ and sodium hydride, followed by ZnCl₂ and finally NaN(SiMe₃)₂ yielded the compound [Zn{N(SiMe₃)₂}₂L¹] (4). The reaction between three equivalents of Zn(C₆F₅)₂·toluene and oxacalix[3]arene (L²H₃) at room temperature formed the compound {[Zn(C₆F₅)]₃L²} (5); heating of 5 in acetonitrile caused the ring opening of the parent oxacalix[3]arene and rearrangement to afford the complex [(L²)Zn₆(C₆F₅)(R)(RH)OH]·5MeCN R = C₆F₅CH₂-(p-ᵗBuPhenolate-CH₂OCH₂–)₂–p-ᵗBuPhenolate-CH₂O⁻)³⁻ (6). The molecular structures of the new complexes 1, 3 and 6, together with that of the known complex 2, whose solid state structure has not previously been reported, have been determined. Compounds 1, 3–5 have been screened for the ring opening polymerization (ROP) of ε-caprolactone (ε-CL) and rac-lactide. Compounds featuring a Zn–C₆F₅ fragment were found to be poor ROP pre-catalysts as they did not react with benzyl alcohol to form an alkoxide. By contrast, compound 4, which contains a zinc silylamide linkage, was the most active of the zinc-based calix[4]arene compounds screened and was capable of ROP at ambient temperature with 65% conversion over 4 h

Use of metal catalysts bearing Schiff base macrocycles for the ring opening polymerization (ROP) of cyclic esters

© 2017 by the authors. Schiff base macrocycles are emerging as useful scaffolds for binding two or more catalytic metals in close proximity. Such coordination chemistry allows for the evaluation of potentially beneficial catalytic cooperative effects. In the field of ring opening polymerization (ROP) of cyclic esters, only a handful of metal systems bound by Schiff base [2 + 2] type macrocycles have been studied. Nevertheless, results to date have, for certain metals, identified some interesting structure activity relationships, whilst for other systems results have revealed particular combinations of metals and macrocycles to be virtually inactive. This perspective review takes a look at two types of recently-reported Schiff base macrocycles that have been employed as pro-ligands in the metal-catalyzed ROP of cyclic esters, specifically ε-caprolactone and rac-lactide

Organoaluminium complexes derived from Anilines or Schiff bases for ring opening polymerization of epsilon-caprolactone, delta-valerolactone and rac-lactide

Reaction of R¹R²CHN=CH(3,5-tBu₂C₆H₂-OH-2) (R¹ = R² = Me L¹H; R¹ = Me, R² = Ph L²H; R¹ = R2 = Ph L³H) with one equivalent of R³3Al (R³ = Me, Et) afforded [(L¹-³)AlR³₂] (L¹, R³ = Me 1, R³ = Et 2; L², R³ = Me 3, R³ = Et 4; L³ R³ = Me 5, R³ = Et 6); complex 1 has been previously reported. Use of the N,O-ligand derived from 2,2/-diphenylglycine afforded either 5 or a by-product [Ph₂NCH₂(3,5-tBu₂C₆H₂-O-2)AlMe₂] (7). The known Schiff base complex [2-Ph₂PC₆H4CH₂(3,5-tBu₂C₃H₂-O-2)AlMe₂] (8) and the product of the reaction of 2-diphenylphosphinoaniline 1-NH₂,2-PPh₂C₆H4 with Me3Al, namely {Ph₂PC₆H4N[(Me₂Al)₂mu-Me](mu-Me₂Al)} (9) were also isolated. For structural and catalytic comparisons, complexes resulting from interaction of Me₃Al with diphenylamine or benzhydrylamine, namely {Ph₂N[(Me₂Al)2mu-Me]} (10) and [Ph₂CHNH(mu-Me₂Al)]₂·MeCN (11), were prepared. The molecular structures of the Schiff pro-ligands derived from Ph₂CHNH₂ and 2,2/-Ph2C(CO₂H)(NH₂), together with complexes 5, 7 and 9 - 11·MeCN were determined. All complexes have been screened for their ability to ring opening polymerization (ROP) epsilon-caprolactone, delta-valerolactone or rac-lactide, in the presence of benzyl alcohol, with or without solvent present. The co-polymerization of epsilon-caprolactone with rac-lactide has also been studied

Organoaluminium complexes of ortho-, meta-, para-anisidines: synthesis, structural studies and ROP of ε-caprolactone (and rac-lactide)

Reaction of Me₃Al (two equivalents) with ortho-, meta- or para-anisidine, (OMe)(NH₂)C₆H₄, affords the complexes {[1,2-(OMe),NC₆H₄(μ-Me₂Al)](μ-Me₂Al)}₂ (1), [1,3-(Me₃AlOMe),NHC₆H₄(μ-Me₂Al)]2 (2) or [1,4-(Me₃AlOMe),NHC₆H₄(μ-Me₂Al)]₂ (3), respectively. The molecular structures of 1–3 have been determined and all three complexes were found to be highly active for the ring opening polymerization (ROP) of ε-caprolactone. 1 was found highly active either with or without benzyl alcohol present; at various temperatures, the activity order 1 > 2 ≈ 3 was observed. For the ROP of rac-lactide results for 1–3 were poor

Multimetallic lithium complexes derived from the acids Ph₂C(X)CO₂H (X = OH, NH₂) : synthesis, structure and ring opening polymerization of lactides and lactones

Reaction of LiOR (R=t-Bu, Ph) with the acids 2,2/-Ph₂C(X)(CO₂H), X=OH (benzH), NH₂ (dpgH) was investigated. For benzH, one equivalent LiOt-Bu in THF afforded [Li(benz)]2⋅2THF (1⋅2THF), which adopts a 1D chain structure. If acetonitrile is used (mild conditions), another polymorph of 1 is isolated; LiOPh also led to 1. Robust work-up afforded [Li₇(benz)₇(MeCN)] 2MeCN THF (2⋅2MeCN⋅THF). Use of LiOt-Bu (2 equivalents) led to {Li₈(Ot-Bu)₂[(benz)](OCPh₂CO₂CPh₂CO2t-Bu)₂(THF)₄} (3), the core of which comprises two open cubes linked by benz ligands. For dpgH, two equivalents of LiOt-Bu in THF afforded [Li6(Ot-Bu)₂(dpg)₂(THF)₂] (4), which contains an Li₂Ov 6-step ladder. Similar reaction of LiOPh afforded [Li₈(PhO)₄(dpg)₄(MeCN)₄] (5). Complexes 1–5 were screened for their potential as catalysts for ring opening polymerization (ROP) of ϵ-caprolactone (ϵ-CL), rac-lactide (rac-LA) and δ-valerolactone (δ-VL). For ROP of ϵ-CL, conversions > 70 % were achievable at 110 °C with good control. For rac-LA and δ-VL, temperatures of at least 110 °C over 12 h were necessary for activity (conversions > 60 %). Systems employing 2 were inactiv

Vanadium(v) phenolate complexes for ring opening homo- and co-polymerisation of ε-caprolactone, L-lactide and rac-lactide

The vanadyl complexes [VO(OtBu)L¹ ] (1) and {[VO(OiPr)]₂ (μ-p-L²ᵖ)} (2) {[VO(OR)]₂ (μ-p-L²ᵐ )} (R = iPr 3, tBu 4) have been prepared from [VO(OR)₃ ] (R = nPr, iPr or tBu) and the respective phenol, namely 2,2′-ethylidenebis(4,6-di-tert-butylphenol) (L¹ H₂ ) or α,α,α′,α′-tetra(3,5-di-tert-butyl-2-hydroxyphenyl–p/m-)xylene-para-tetraphenol (L2p/mH₄). For comparative studies, the known complexes [VO(μ-OnPr)L¹]₂ (I), [VOL³ ]₂ (II) (L³H₃ = 2,6-bis(3,5-di-tert-butyl-2-hydroxybenzyl)-4-tert-butylphenol) were prepared. An imido complex {[VCl(Np-tolyl)(NCMe)]₂(μ-p-L²ᵖ)} (5) has been prepared following work-up from [V(Np-tolyl)Cl₃ ], L²ᵖH₄ and Et₃ N. The molecular structures of complexes 1–5 are reported. Complexes 1–5 and I and II have been screened for their ability to ring open polymerise ε-caprolactone, L-lactide or rac-lactide with and without solvent present. The co-polymerization of ε-caprolactone with L-lactide or rac-lactide afforded co-polymers with low lactide content; the reverse addition was ineffective

Aluminum amine-bis(phenolate) complexes for ring-opening polymerization of rac-lactide and ε-caprolactone

Five aluminum-based amine-bis(phenolate) complexes, three of them novel, with variation of the pendant donor arm were synthesized in excellent yields, and characterized by NMR spectroscopy and X-ray crystallography. The quantitative conversion of the aluminum alkyl species to the corresponding benzyl alkoxide was achieved by the addition of 1 mol eq. of benzyl alcohol, and was confirmed by 1H NMR spectroscopy. The aluminum alkoxides were excellent mediators for the ring-opening polymerization (ROP) of rac-lactide, yielding atactic poly(lactic acid), having excellent correlation between theoretical and calculated molecular weights accompanied by narrow molecular weight distributions. ROP of ε-caprolactone by the aluminum alkoxides showed modest control at 50°C in toluene, but much greater control was achieved when polymerizations were conducted at 25°C, with narrower molecular weight distributions observed in some cases. A relationship between the complex pendant donor arm and the resulting activity in the ROP of both rac-lactide and ε-caprolactone is discussed

Ring opening polymerization of lactides and lactones by multimetallic alkyl zinc complexes derived from the acids Ph₂C(X)CO₂2H (X = OH, NH₂ )

The reaction of the dialkylzinc reagents R₂Zn with the acids 2,2-Ph₂C(X)(CO₂H), where X = NH₂, OH, i.e. 2,2′-diphenylglycine (dpgH) or benzilic acid (benzH2), in toluene at reflux temperature afforded the tetra-nuclear ring complexes [RZn(dpg)]₄, where R = Me (1), Et (2), 2-CF₃C₆H₄ (3), and 2,4,6-F₃C₆H₂ (4); complex 2 has been previously reported. The crystal structures of 1·(2MeCN), 3 and 4·(4(C₇H₈)·1.59(H₂O)) are reported, along with that of the intermediate compound (2-CF₃C₆H₄)3B·MeCN and the known compound [ZnCl₂(NCMe)₂]. Complexes 1–4, together with the known complex [(ZnEt)₃(ZnL)₃(benz)₃] (5; L = MeCN), have been screened, in the absence of benzyl alcohol, for their potential to act as catalysts for the ring opening polymerization (ROP) of ε-caprolactone (ε-CL), δ-valerolactone (δ-VL) and rac-lactide (rac-LA); the co-polymerization of ε-CL with rac-LA was also studied. Complexes 3 and 4 bearing fluorinated aryls at zinc were found to afford the highest activities

Metallocalixarene catalysts: α-olefin polymerization and ROP of cyclic esters

This perspective review discusses metallocalix[n]arene complexes that have been employed in either α-olefin polymerization or in the ring opening polymerization (ROP) of cyclic esters over the last 5 years. Synthesis, molecular structure and catalytic potential are discussed. For α-olefin polymerization, systems based on early transition metals in combination with calix[n]arenes (n = 4, 6 or 8), depleted calix[4]arenes or thia/sulfinyl/sulfonyl calix[4]arenes have been reported, and in some cases, are highly active. For the ROP studies, a number of the systems, typically of the early transition metals, only exhibit activity under robust conditions, whereas other systems, for example those of magnesium, demonstrate exceptional activity, immortal behaviour and intriguing stereoselectivity