Juan Fernández-Baeza

Nonisocyanate polyurethane materials with pending alcohol groups in the polymeric chain were synthesized by polyaddition reaction of bis(cyclic carbonates) onto diamines. For the platform molecule, 1,4-butanediol bis(glycidyl ether carbonate) (BGBC, 1) was used. The polyaddition reaction of 1 onto a wide range of diamines with different electronic and physical properties was explored. All PHUs were obtained quantitatively after 16 h at 80 °C temperature in MeCN as solvent. The low nucleophilicity of L-lysine has proven unable to ring-open the cyclic carbonate and, thus, no reaction occurred. The addition of DBU or TBD as the catalyst was tested and allows the obtention of the desired PHU. However, the presence of strong bases also led to the formation of polyurea fragments in the new PHU. The different poly(hydroxyurethane) materials were characterized using a wide range of spectroscopic techniques such as NMR, IR, MALDI-ToF, and using GPC studies. The thermal properties of the NIPUs were investigated by DSC and TGA analyses. Moreover, reactions employing different monomer ratios were performed, obtaining novel hydroxycarbamate compounds. Finally, sequential and one-pot experiments were also carried out to synthesize the PHUs polymers in one-step reaction.

The direct reaction of the highly sterically demanding acetamidinate-based NNN′-scorpionate protioligand Hphbp^tamd [Hphbp^tamd = N,N′-di-p-tolylbis(3,5-di-tertbutylpyrazole-1-yl)acetamidine] with one equiv. of ZnMe₂ proceeds in high yield to the mononuclear alkyl zinc complex [ZnMe(κ³-phbp^tamd)] (1). Alternatively, the treatment of the corresponding lithium precursor [Li(phbp^tamd)(THF)] with ZnCl₂ yielded the halide complex [ZnCl(κ³-phbptamd)] (2). The X-ray crystal structure of 1 confirmed unambiguously a mononuclear entity in these complexes, with the zinc centre arranged with a pseudotetrahedral environment and the scorpionate ligand in a κ³-coordination mode. Interestingly, the inexpensive, low-toxic and easily prepared complexes 1 and 2 resulted in highly efficient catalysts for the ring-opening polymerisation of lactides, a sustainable bio-resourced process industrially demanded. Thus, complex 1 behaved as a single-component robust initiator for the living and immortal ROP of rac-lactide under very mild conditions after a few hours, reaching a TOF value up to 5520 h⁻¹ under bulk conditions. Preliminary kinetic studies revealed apparent zero-order dependence on monomer concentration in the absence of a cocatalyst. The PLA materials produced exhibited narrow dispersity values, good agreement between the experimental M_n values and monomer/benzyl alcohol ratios, as well as enhanced levels of heteroselectivity, reaching P_s values up to 0.74.

The catalytic activity and high selectivity reported by bimetallic heteroscorpionate acetate zinc complexes in ring-opening copolymerization (ROCOP) reactions involving CO₂ as substrate encouraged us to expand their use as catalysts for ROCOP of cyclohexene oxide (CHO) and cyclic anhydrides. Among the catalysts tested for the ROCOP of CHO and phthalic anhydride at different reaction conditions, the most active catalytic system was the combination of complex 3 with bis(triphenylphosphine)iminium as cocatalyst in toluene at 80 °C. Once the optimal catalytic system was determined, the scope in terms of other cyclic anhydrides was broadened. The catalytic system was capable of copolymerizing selectively and efficiently CHO with phthalic, maleic, succinic and naphthalic anhydrides to afford the corresponding polyester materials. The polyesters obtained were characterized by spectroscopic, spectrometric, and calorimetric techniques. Finally, the reaction mechanism of the catalytic system was proposed based on stoichiometric reactions.

Despite the great interest in zinc catalysis for hydroelementation reactions, the use of zinc complexes as catalysts for the hydroalkoxylation of alkynyl alcohols has not been reported to date. Scorpionate zinc complexes have been successfully designed as precatalysts for the hydroalkoxylation reaction of alkynyl alcohols under mild reaction conditions. Zinc amide complex 8 has been shown to be an excellent precatalyst for the highly selective intramolecular hydroalkoxylation process to yield the corresponding exocyclic enol ethers. Kinetic studies have been performed and confirmed that reactions are first-order in [catalyst] and zero-order in [alkynyl alcohol]. NMR spectroscopy and X-ray diffraction analysis provided evidence for the formation of an alkynyl zinc compound which has been shown to be a key intermediate in the hydroalkoxylation process. On the basis of the experimental results, a catalytic cycle is proposed.

New mono- and dinuclear chiral alkoxide/thioalkoxide NNO-scorpinate zinc complexes were easily synthesized in very high yields, and characterized by spectroscopic methods. X-ray diffraction analysis unambiguously confirmed the different nuclearity of the new complexes as well as the variety of coordination modes of the scorpionate ligands. Scorpionate zinc complexes 2, 4 and 6 were assessed as catalysts for polycarbonate production from epoxide and carbon dioxide with no need for a co-catalyst or activator under mild conditions. Interestingly, at 70 °C, 10 bar of CO₂ pressure and 1 mol % of loading, the dinuclear thioaryloxide [Zn(bpzaepe)₂{Zn(SAr)₂}] (4) behaves as an efficient and selective one-component initiator for the synthesis of poly(cyclohexene carbonate) via ring-opening copolymerization of cyclohexene oxide (CHO) and CO₂, affording polycarbonate materials with narrow dispersity values.

Two new derivatives of the bis(3,5-dimethylpyrazol-1-yl)methane modified by introduction of organosilyl groups on the central carbon atom, one of which bearing a chiral fragment, have been easily prepared. We verified the potential utility of these compounds through the reaction with [Zr(NMe₂)₄] for the preparation of novel zirconium complexes in which an ancillary bis(pyrazol-1-yl)methanide acts as a robust monoanionic tridentate scorpionate in a κ³-NNC chelating mode, forming strained four-membered heterometallacycles. These κ³-NNC-scorpionate zirconium amides were investigated as catalysts in combination with tetra-n-butylammonium bromide as cocatalyst for CO₂ fixation into five-membered cyclic carbonate products. The study has led to the development of an efficient zirconium-based bicomponent system for the selective cycloaddition reaction of CO₂ with epoxides. Kinetics investigations confirmed apparent first-order dependence on the catalyst and cocatalyst concentrations. In addition, this system displays very broad substrate scope, including mono- and disubstituted substrates, as well as the challenging biorenewable terpene derived limonene oxide, under mild and solvent-free conditions.

Novel bimetallic zinc acetate complexes supported by heteroscorpionate ligands have been developed for the ring-opening copolymerization of cyclohexene oxide and CO₂ and the terpolymerization of cyclohexene oxide, phthalic anhydride, and CO₂. Heteroscorpionate ligands precursors L₁–L₃ were reacted with two equivalents of zinc acetate to afford the dinuclear zinc complexes [{Zn(κ³-bpzappe)}(μ-O₂CCH₃)₃-{Zn(HO₂CCH₃)}] (1), [{Zn(κ³-bpzbdmape)}(μ-O₂CCH₃)₃-{Zn(HO₂CCH₃)}] (2), and [{Zn(κ³-bpzbdeape)}(μ-O₂CCH₃)₃{Zn(HO₂CCH₃)}] (3) in excellent yields. The molecular structure of these compounds was determined spectroscopically and confirmed by X-ray diffraction analysis. Zinc acetate complexes 1–3 were screened as catalysts for the copolymerization of cyclohexene oxide and CO₂ to produce poly(cyclohexene)carbonate, and complex 3 was found to be the most active catalyst for this process in the absence of a cocatalyst. Furthermore, the terpolymerization of cyclohexene oxide, phthalic anhydride, and CO₂ was studied using the combination of complex 3 and 4-dimethylaminopyridine as catalyst system yielding the corresponding polyester-polycarbonate materials.

The binuclear aluminum complexes [AlR ₂ (κ ² - NN ′;κ ² - NN ′)AlR ₂ ] with TBAB/PPNCl behave as excellent systems for cyclic carbonate formation from CO ₂ with challenging epoxides.