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Volumn 133, Issue 17, 2011, Pages 6761-6779

Pd-catalyzed copolymerization of methyl acrylate with carbon monoxide: Structures, properties and mechanistic aspects toward ligand design

Author keywords

[No Author keywords available]

Indexed keywords

ACRYLIC ESTER; ALTERNATING COPOLYMERIZATION; BACK-DONATION; BIDENTATE LIGANDS; CATALYTIC CYCLES; DIPHOSPHINES; ELECTRON DEFICIENT OLEFINS; GLASS TRANSITION TEMPERATURE; LIGAND DESIGN; MECHANISTIC ASPECTS; METHYL ACRYLATES; RATE DETERMINING STEP; REGIOREGULARITY; REVERSIBLE INSERTION; STEREOCENTERS; THEORETICAL INVESTIGATIONS; TRANSITION STATE;

EID: 79955433027     PISSN: 00027863     EISSN: 15205126     Source Type: Journal    
DOI: 10.1021/ja2003268     Document Type: Article
Times cited : (61)

References (147)
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    • For the mechanism of the formation of the linear polyethylene catalyzed by Pd phosphine-sulfonate complexes, see: (a) Noda, S.; Nakamura, A.; Kochi, T.; Chung, L. W.; Morokuma, K.; Nozaki, K. J. Am. Chem. Soc. 2009, 131, 14088-14100
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    • Very recently, Jordan proposed another possible cis / trans isomerization mechanism: (b) Conley, M. P.; Jordan, R. F. Angew. Chem. Int. Ed. 2011, 50, 3744-3746
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    • Slight amount of Pd black was observed after the reaction. See also ref 39.
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    • The complex 2a can copolymerize ethylene and MA with low MA ratio (unpublished resuls, see also references (12d) for a result by a pyridine adduct complex). Considering the copolymerization of MA with CO proceeds in alternating fashion, coordination of MA should occur in each catalytic cycle. Thus, MA/CO copolymerization should be more sluggish than ethylene/CO copolymerization with low MA ratio.
    • The complex 2a can copolymerize ethylene and MA with low MA ratio (unpublished resuls, see also references (12d) for a result by a pyridine adduct complex). Considering the copolymerization of MA with CO proceeds in alternating fashion, coordination of MA should occur in each catalytic cycle. Thus, MA/CO copolymerization should be more sluggish than ethylene/CO copolymerization with low MA ratio.
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    • Recently, the reactivity of methyl methacrylate with Pd phosphine-sulfonate complex was studied in detail, see: Runzi, T.; Guironnet, D.; Göttker-Schnetmann, I.; Mecking, S. J. Am. Chem. Soc. 2010, 132, 16623-16630
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    • 13C NMR showed broad signal at 110.6-115.5 ppm which is typical region for spiro quarternary carbon.
    • 13C NMR showed broad signal at 110.6-115.5 ppm which is typical region for spiro quarternary carbon.
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    • 1H NMR spectrum.
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    • 2, 25% of the methine protons were exchanged with deuterium after 4 h at room temperature.
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    • If the stereochemistry of poly(methyl acrylate- alt -CO) is thermodynamically controlled and the split signals at low temperature are originated from the fluctuation of higher-order structure, it is still unclear whether the regiochemistry of poly(t -butyl acrylate- alt -CO) is controlled or not.
    • If the stereochemistry of poly(methyl acrylate- alt -CO) is thermodynamically controlled and the split signals at low temperature are originated from the fluctuation of higher-order structure, it is still unclear whether the regiochemistry of poly(t -butyl acrylate- alt -CO) is controlled or not.
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    • Recently, we reported terpolymerization of styrene/vinyl acetate/CO and styrene/methyl acrylate/CO by using the same catalyst, see
    • Recently, we reported terpolymerization of styrene/vinyl acetate/CO and styrene/methyl acrylate/CO by using the same catalyst, see: Kageyama, T.; Ito, S.; Nozaki, K. Chem. Asian J. 2011, 6, 690-697
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    • However, preliminary XRD analyses showed tiny signals for poly(MA- alt -CO) and poly(CO- alt -(ethylene; MA)). The results indicate the possibility of being crystalline polymer. Further investigations for the physical properties are in progress.
    • However, preliminary XRD analyses showed tiny signals for poly(MA- alt -CO) and poly(CO- alt -(ethylene; MA)). The results indicate the possibility of being crystalline polymer. Further investigations for the physical properties are in progress.
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    • It is known that the activity for the copolymerization of ethylene with CO is higher when diphenylphosphinopropane (DPPP) is used than that of DPPE (ref 1a). However, we chose DPPE for the discussion because of the decreased degrees of freedom of the ligand for the theoretical study. Note that the calculated energy required for the rate-determining step was 38.9 kcal/mol by utilizing DPPP as a ligand, which is even higher than that of DPPE. See section 7.
    • It is known that the activity for the copolymerization of ethylene with CO is higher when diphenylphosphinopropane (DPPP) is used than that of DPPE (ref 1a). However, we chose DPPE for the discussion because of the decreased degrees of freedom of the ligand for the theoretical study. Note that the calculated energy required for the rate-determining step was 38.9 kcal/mol by utilizing DPPP as a ligand, which is even higher than that of DPPE. See section 7.
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    • 3) were inert to the insertion of CO. The Pd-C and Pd-O bond distances, determined by X-ray diffraction, are at the short end of the ranges observed in the analogous non-halogenated five-membered chelate complexes.
    • 3) were inert to the insertion of CO. The Pd-C and Pd-O bond distances, determined by X-ray diffraction, are at the short end of the ranges observed in the analogous non-halogenated five-membered chelate complexes.
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    • 4 group on phosphorus atom in 3c makes this comparison imperfect.
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    • Because 2D NMR spectra were not applicable under the high pressure conditions, these signals were characterized by comparisons to the literature. Note that our high-pressure NMR apparatus is not applicable at higher temperature.
    • Because 2D NMR spectra were not applicable under the high pressure conditions, these signals were characterized by comparisons to the literature. Note that our high-pressure NMR apparatus is not applicable at higher temperature.
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    • 13C NMR, the palladium complexes gradually decomposed to result in the formation of some Pd black.
    • 13C NMR, the palladium complexes gradually decomposed to result in the formation of some Pd black.
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    • Comparison of B3LYP/6-31G* with Lanl2dz and B3LYP/6-311+G * with SDD +f is described in Supporting Information. Because the copolymerization was conducted under neat condition, PCM calculation was not performed to avoid inappropriate discussion. Largely, B3LYP/6-31G* with Lanl2dz in gas phase sufficiently match with our experiments. See also ref 14.
    • Comparison of B3LYP/6-31G* with Lanl2dz and B3LYP/6-311+G * with SDD +f is described in Supporting Information. Because the copolymerization was conducted under neat condition, PCM calculation was not performed to avoid inappropriate discussion. Largely, B3LYP/6-31G* with Lanl2dz in gas phase sufficiently match with our experiments. See also ref 14.
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    • For example of the theoretical studies employing other unsymmetrical bidentate ligands in coordination-insertion polymerizations, see: Nozaki, K.; Sato, N.; Tonomura, Y.; Yasutomi, M.; Takaya, H.; Hiyama, T.; Matsubara, T.; Koga, N. J. Am. Chem. Soc. 1997, 119, 12779-12795
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    • trans regardless of the ketone coordination.
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    • It was expected from these calculations that the IR spectrum of these carbonyl complexes would give us important implication. Thus, we conducted some experiments to take IR spectrum of carbonyl complexes, however, carbonyl complexes were not isolable and the signals in IR spectrum under CO atmosphere were too complicated to assign for both Pd phosphine-sulfonate and Pd dppe systems.
    • It was expected from these calculations that the IR spectrum of these carbonyl complexes would give us important implication. Thus, we conducted some experiments to take IR spectrum of carbonyl complexes, however, carbonyl complexes were not isolable and the signals in IR spectrum under CO atmosphere were too complicated to assign for both Pd phosphine-sulfonate and Pd dppe systems.
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    • trans.
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    • Similar transition states were expected in ethylene/CO copolymerization, see: Margl, P.; Ziegler, T. J. Am. Chem. Soc. 1996, 118, 7337-7344
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    • trans involving CO and a direct insertion of CO at apical position could not be found.
    • trans involving CO and a direct insertion of CO at apical position could not be found.
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    • cis(5a), they were not observed in the experiment in Figure 5. This inconsistence between experiments and calculation may be attributed to the less inaccurate estimation of entropy
    • cis(5a), they were not observed in the experiment in Figure 5. This inconsistence between experiments and calculation may be attributed to the less inaccurate estimation of entropy
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    • PP became unstable for 3.9 kcal/mol without ketone coordination. This tendency is contrastive to the neutral Pd phosphine-sulfonate case whose stabilities are not so influenced by the existence of internal ketone coordination. See also ref 44.
    • PP became unstable for 3.9 kcal/mol without ketone coordination. This tendency is contrastive to the neutral Pd phosphine-sulfonate case whose stabilities are not so influenced by the existence of internal ketone coordination. See also ref 44.
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    • Comparative studies by theoretical calculations of the preference between 2,1- and 1,2-insertion with vinyl acetate/CO copolymerization are now in progress. See ref 10.
    • Comparative studies by theoretical calculations of the preference between 2,1- and 1,2-insertion with vinyl acetate/CO copolymerization are now in progress. See ref 10.
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    • trans could not be located either. See ref 54.
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    • cis, -7.9/-2.4 kcal/mol on the basis of Pd(CO)COMe), double CO insertion is unlikely. See also: ref 1.
    • cis, -7.9/-2.4 kcal/mol on the basis of Pd(CO)COMe), double CO insertion is unlikely. See also: ref 1.
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    • cis as a standard for the following discussion because the differences are quite slight and within the error of the calculation. See also ref 54.
    • cis as a standard for the following discussion because the differences are quite slight and within the error of the calculation. See also ref 54.
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    • Some studies of novel ligands inspired by phosphine-sulfonate ligands, see
    • Some studies of novel ligands inspired by phosphine-sulfonate ligands, see: Reisinger, C. M.; Nowack, R. J.; Volkmer, D.; Rieger, B. Dalton Trans. 2007, 272-278
    • (2007) Dalton Trans. , pp. 272-278
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    • Some applications of phosphine-sulfonate ligands to the other organic reactions, see
    • Some applications of phosphine-sulfonate ligands to the other organic reactions, see: Schultz, T.; Pfaltz, A. Synthesis 2005, 1005-1011
    • (2005) Synthesis , pp. 1005-1011
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    • SP-4-3" represents the stereochemical information of the square planar complex. See: IUPAC; Blackwell Scientific Publications: Oxford.
    • "SP-4-3" represents the stereochemical information of the square planar complex. See: IUPAC Nomenclature of Inorganic Chemistry, Recommendations 2005; Blackwell Scientific Publications: Oxford, 2005.
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    • Revision C02; Gaussian, Inc.: Wallingford, CT.
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