Frediani, Marco

Giachi, Guido

Oberhauser, W.

Passaglia, E.

English

Florence Research

  PLA- and PCL-based Pd(II)-Pyridine Macrocomplexes  G. Giachi1, M. Frediani1, W. Oberhauser2, E. Passaglia3 1Department of Chemistry, University of Florence, via della Lastruccia 13, 50019 Sesto Fiorentino (Italy) -  marco.frediani@unifi.it 2ICCOM-CNR, Area di Ricerca di Firenze, via Madonna del Piano 10, 50019 Sesto Fiorentino (italy) 3ICCOM-CNR, UOS Pisa, Area della Ricerca, via Moruzzi 1, 56124 Pisa,(Italy).  Abstract. Pyridine end-capped L-poly(lactide), L,D-poly(lactide) and poly(caprolactone) were synthesized by 4-hydroxymethyl-piridine initiated ROP and employed as macroligands for the square-planar coordination of Pd(II) ions. PdCl2 macrocomplexes with trans-stereochemistry were obtained and further reacted to give homo- and heteroleptic star-shaped products. Palladium bis-acetate macrocomplexes were synthesized and employed as recyclable homogeneous catalysts for aerobic oxidation reactions.) Homo- and heteroleptic V-shaped Pd(II)(allyl) macrocomplexes were synthesized via a suitable Pd(II) intermediate. All new compounds were characterized by 1H- and 13C-NMR, UV/Vis-spectroscopy, GPC and DSC analyses.   1. INTRODUCTION  The synthesis of metallo-supramolecular block-copolymers with new tunable physical and chemical properties (e.g. light absorption/emission, viscosity/adhesion) is gaining increasing interest.1-3 In particular, metallo-supramolecular block copolymers linked by a metal-ligand complex have seen important progresses, exploiting: (i) the coordination geometry of the metal centre to impart new polymer architectures;1-9 (ii) the electronic property of the metal centre characterized by its oxidation state;10-13 (iii) the much lower stability of coordination bonds compared to covalent bonds in order to reversibly control the macroligand dissociation and association to the metal centre.1-3,14 Generally, metallo-supramolecular polymers are accessible by either the coordination of preformed macroligands to a metal ion, or by the use of a suitable metal complex as the initiator for the polymerization reaction.1-3 The most employed ligands in metallo-supramolecular chemistry are terpyridine-1-5,12,14 or bipyridine-based,6,10 while pyridines are rarely used.13 The nitrogen ligand end-capped polymers were mostly coordinated to Fe(II) and Ru(II), leading to linear or star-shaped polymer architectures.1-3   2. RESULTS AND DISCUSSION  The Sn(Oct)2 (Oct = 2-ethylhexanoate)-catalyzed ring opening polymerization (ROP)15 of L- and rac-lactide and -caprolactone carried out in bulk in the presence of 4-PyCH2OH gave the 4-pyridinemethylene-end-capped L-poly(lactide) macroligand L1 (Mn = 3280 g/mol, PDI = 1.33); the rac-poly(lactide) macroligand L2 (Mn = 3700 g/mol, PDI = 1.54)  and the PCL macroligand L3 in 84, 75 and 60% yield, respectively. The esterification of 4-PyCH2OH has been proved by a 13C NMR singlet centered at 64.97 ppm, which was   assigned to the 4-PyCH2O carbon atom. In addition, the absence of the 13C NMR singlet assigned to the carboxylic acid carbon atom at ca. 171.60 ppm combined with the lack of a 1H NMR singlet at 4.74 ppm assigned to PyCH2OH is a further valuable prove of the occurred end-capping of poly(lactide). The 1:2 stoichiometric reaction between PdCl2 and L1 or L2 carried out in a 3:1 solvent mixture of CH2Cl2 and DMF gave trans-[PdCl2(L1)2] (1a) and trans-[PdCl2(L2)2] (2), respectively as light brown powders with ca. 80% yield. The 1:2 stoichiometric reaction between PdCl2 and L3 carried out in a 1:1 solvent mixture of CH2Cl2 and DMF gave trans-[PdCl2(L3)2] (3) as a brown powder with ca. 85% yield. The 1:2 stoichiometric reaction between Pd(OAc)2 and L1 carried out in CH2Cl2 gave trans-[Pd(OAc)2(L1)2] (1b) as a beige powder with 95% yield (Scheme 1a).   Scheme 1: Synthesis of Pd(II) macrocomplexes.   1H NMR and 13C1H NMR spectra of 1a, 1b, 2 and 3, acquired in CD2Cl2, showed for the ortho-hydrogen atoms of the pyridine moiety a coordination shift of ca. 0.2 ppm. GPC- measurements carried out on CHCl3 solutions of 1a, 1b, 2 and 3 proved a two-fold increase of the molecular weight compared to the corresponding uncoordinated macroligand. The coordination of the pyridine moieties trans to each other in 1a, 1b, 2 and 3 has been confirmed by acquiring UV/Vis spectra of the latter macrocomplexes in CHCl3 and using trans-[PdCl2(4-EtPy)2] and trans-[Pd(OAc)2(4-EtPy)2] (4-EtPy = 4-ethylpyridine) as reference compounds. The X-ray structure of these reference compounds confirmed the trans-coordination of the pyridine ligand to palladium. The 1:1 stoichiometric reaction between [PdCl(3-ally)]2 and L1 gave 4 as beige powder with 68% yield (Scheme 1b). 1H and 13C NMR spectra for 4, acquired in CD2Cl2 at room temperature and -60 °C confirmed the asymmetric coordination of the allyl-moiety, due to the presence of different ligands (i.e. chloride and pyridine moiety) coordinating trans to it.16 The reaction of 4 with either L1, L2 or L3 in the presence of NaBAr’4 (Ar’ = 3,5-bis(trifluoromethyl)phenyl) gave the   monocationic, V-shaped, homo- and heteroleptic macrocomplexes 5, 6 and 7, respectively. The substitution of the chloride atom in 4 by L1, L2 or L3 was confirmed by 1H and 13C1H NMR spectra, acquired at room temperature and at -60 °C. The homoleptic star-shaped Pd(II) macrocomplexes (i.e. 8, 9 and 12) were obtained upon reaction of 1, 2 and 3 with two molequiv. of L1, L2 and L3, respectively in the presence of Ag(SbF6); the heteroleptic PLA-based macrocomplexes (i.e. 10, 11) were obtained by the reaction of 1a with two molequiv. of L2 in the presence of either Ag(SbF6) or Ag(OTs) (OTs = p-Toluenesulfonate), while the heteroleptic PLA/PCL macrocomplex 13 was obtained by the reaction of 3 with two molequiv. of L1 in the presence of Ag(SbF6) (Scheme 1c). All star-shaped macrocomplexes were obtained as light brown powders with not yet optimized yields ranging from 45 to 60%. 1H and 13C1H NMR spectra acquired for the star-shaped macrocomplexes confirmed the symmetric coordination of the pyridine moieties to the metal centre. The successful coordination of four macroligands to the same Pd(II) centre has been proved by: (i) the 1H NMR integral ratio between the aromatic tosylate and pyridine hydrogen atoms in 11; (ii) the reaction of 8 with two molequiv. of 1,2-bis(diphenylphosphanyl)ethane (dppe) in CD2Cl2 leading to uncoordinated L1 and [Pd(dppe)2](SbF6)2, which was the only phosphorus containing compound. Unfortunately, the charged complexes proved to be not stable during GPC-analysis, due to the presence of strong shear forces stemming from high-performance packing in size exclusion chromatography.17 The stepwise de-coordination of macroligands from V- and star-shaped macrocomplexes has been studied by means of NMR-spectroscopy. To this purpose, 5 was reacted with one molequiv. of [N(n-Bu)4]Cl in CD2Cl2 to give a 1:1 mixture of 4 and uncoordinated L1. The corresponding 1H NMR spectrum, acquired at room temperature, showed for the pyridine-moiety two broad singlets centred at 7.35 and 8.72 ppm, due to a dynamic equilibrium between 4 and L1 at room temperature. Accordingly, the corresponding 1H NMR spectrum, acquired at -70 °C, showed for the ortho-hydrogen atoms of 4 and L1 two distinct 1H NMR doublets at 8.77 and 8.62 ppm, respectively. Upon reaction of 5 with one molequiv. of dppe, [Pd(3-allyl)(dppe)]BAr’4 was formed under the quantitative release of L1 as proved by the corresponding 1H NMR spectrum. The addition of two molequiv. of [N(n-Bu)4]Cl to a CD2Cl2 solution of 8 led to a 1:1 mixture of 1a and uncoordinated L1. The successive addition of two molequiv. of PPh3 to the latter NMR solution brought about the quantitative transformation of 1a into trans-[PdCl2(PPh3)2] and uncoordinated L1. From a perusal of DSC results arises that: (i) the homoleptic macrocomplexes containing L1 (i.e. 1, 5 and 8) showed a higher melting (Tm) and crystallization temperature (Tc) compared to L1, due to an increase of the molecular weight; (ii) 8 showed the lowest crystallinity (c), which is mainly due to the higher number of end groups compared to 1a and 5 and to the presence of two counter-anions; (iii) the heteroleptic macrocomplexes 6, 10 and 11 showed a significantly lower value of crystallinity compared to the corresponding homoleptic counterpart, confirming the influence of L2  on the crystallization behaviour of L1 in the macrocomplexes; (iv) L2 and 9 were found to be completely amorphous; (v) 7 and 13 show crystallinity of both PLA and PCL, each with its own characteristic transition temperatures. The acetate-containing macrocomplex 1b was tested as catalyst precursor under homogeneous catalytic conditions (i.e. 4bar of air; toluene; 70°C; precat/substrate ratio = 1:1600) for the aerobic oxidation of primary and secondary alcohols and its catalytic activity was compared with that of the reference compound trans-[Pd(OAc)2(4-EtPy)2]. Due to the solubility properties of PLA, 1b was easily separated from the reaction solution by precipitation, thus combining the advantages of homo- and heterogeneous catalysis.   Experiments aiming at the formation of macroligand-stabilized Pd(0)-nanoparticles and their use in C-C coupling reactions are in progress in our laboratory.    3. CONCLUSIONS  In summary, we successfully synthesized 4-pyridinemethylene-end-capped L- and LD-poly(lactide) and poly(caprolactone), which was coordinated for the first time to Pd(II) forming neutral linear, monocationic V- and bis-cationic star-shaped macrocomplexes. The occurred metal coordination has been proved in solution by NMR-, UV/Vis-spectroscopy and in the solid state by DSC. The reversibility of the macroligand coordination was demonstrated upon reactions of the macrocomplexes with appropriate ligands (i.e. chloride and phosphanes). The easy stepwise synthesis of the Pd-macrocomplexes allowed the formation of heteroleptic species, which combined poly L-poly(lactide) with LD-poly(lactide) and poly(caprolactone). The Pd acetate-based macrocomplex has been successfully used for the aerobic oxidation of alcohols. Research is in progress to further investigate the solid-state properties of this novel class of polymers.   REFERENCES  [1] Schubert, U. S.; Heller, M. Chem. Eur. J. (2001), 7, 5253-5259. [2] Shunmugam, R.; Gabriel, G. J.; Aamer, K. A.; Tew, G. N. Macromol. Rapid Commun. (2010), 31, 784-793. [3] Fustin, C.-A.; Guillet, P.; Schubert, U. S.; Gohy, J.-F. Adv. Mater. (2007), 19, 1665-1673. [4] Zhou, G.; Harruna, I. I. 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PLA- and PCL-based Pd(II)-Pyridine Macrocomplexes

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PLA- and PCL-based Pd(II)-Pyridine Macrocomplexes

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