Andrew Yeung CHEM636

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1 Andrew Yeung CHEM636

2 Scope verview olyketones and their synthesis Timeline of development Catalyst selection alladium vs. nickel Ligands Mechanism Initiation & termination ropagation

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4 roperties Low T g of 15 C, high T m of 257 C (K-E) olar ketone groups give strong inter-chain forces, backbone allows flexibility Resistant to organic solvents, impermeable to gases Easily recycled rone to UV degradation (C=) n Drent, E.; Mul, W..; Smaardijk, A. A., olyketones. In Encyclopedia of olymer Science and Technology, John Wiley & Sons, Inc.: 2002.

5 Applications Hoses for automotive, food and medical applications n Flame retardant materials Metal-replacement plastics Drent, E.; Mul, W..; Smaardijk, A. A., olyketones. In Encyclopedia of olymer Science and Technology, John Wiley & Sons, Inc.: G. Morrison, Materials and Assembly, Mechanical Engineering, May 1999, Nelco roducts, Inc.; Victrex USA, Inc.

6 Feedstock + C R n n n R = H,, C 6 H 5, etc. α-lefins (ethylene, propylene, styrene, etc.) Functionalized α-olefins (CH 2 H, CH 2 CN, CH) Internal olefins are less reactive (norbornene, norbornadiene) Terpolymerization can modify properties (typ. 6 % propylene for Carilon) Carbon monoxide Drent, E.; Mul, W..; Smaardijk, A. A., olyketones. In Encyclopedia of olymer Science and Technology, John Wiley & Sons, Inc.: 2002.

7 Timeline of development h h d 2+ 2 X R 3 R 3 d Cl Cl h h 1967 First d(ii) catalyst reported by Gough at ICI 1983 Discovery of high-yielding d catalysts at Shell 1996 Shell commercialized polyketones ( Carilon ) 1940s C/C 2 H 4 copolymerization first observed by Walter Reppe C 2 H 4 + C K 2 Ni(CN) 4 H Drent, E.; Mul, W..; Smaardijk, A. A., olyketones. In Encyclopedia of olymer Science and Technology, John Wiley & Sons, Inc.: G. Morrison, Materials and Assembly, Mechanical Engineering, May 1999, n H

8 Interesting observations Non-chelating phosphine complexes give side products, e.g. methyl propionate erfect co-polymerization (no polyethylene or polycarbonyl defects) + C [d] Bianchini, C.; Meli, A. Coord. Chem. Rev. 2002, 225 (1-2), Drent, E.; Budzelaar,. H. M. Chem. Rev. 1996, 96, 663.

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10 alladium or nickel? h h d + h h C H H h h d + H h h h h d h h alladium catalysts are most well-studied, used industrially Deactivation via hydride Benzoquinone helpful as a sacrificial oxidant H C h h d h h h h d 2+ h h h h d h h Shultz, C. S.; DeSimone, J. M.; Brookhart, M. rganometallics 2000, 20, 16. Bianchini, C.; Meli, A. Coord. Chem. Rev. 2002, 225, 35.

11 alladium or nickel? Nickel catalysts are attractive less expensive, already used for SH process (ethylene oligomerization) However Despite lower barriers to migratory insertion, catalyst fails because the catalytic resting state is too stable Different mechanism five-coordinate resting state C must be introduced late it poisons Ni(II) h h h d + C h h h Ni + C h h Shultz, C. S.; DeSimone, J. M.; Brookhart, M. rganometallics 2000, 20, 16.

12 Monodentate vs. bidentate ligands Monodentate phosphines undergo cis/trans isomerization d [ ] cis/trans d [ ] When phosphines are mutually trans, solvolysis is a competing reaction Bidentate phosphines do not suffer from this problem + H H d [ ] Drent, E.; Budzelaar,. H. M. Chem. Rev. 1996, 96, 663.

13 Length of alkylidene bridge Ligand n roductivity (g polymer/g d h) n h 2 (CH 2 )h h 2 (CH 2 ) 2 h h 2 (CH 2 ) 3 h h 2 (CH 2 ) 4 h h 2 (CH 2 ) 5 h h 2 (CH 2 ) 6 h dppp ligand experimentally determined to be best No clear explanation for this effect Chelate ring size of 6 is best Ring size affects catalyst stability, barriers to migratory insertion, kinetic stability of intermediates, etc. Bianchini, C.; Meli, A. Coord. Chem. Rev. 2002, 225 (1-2),

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15 Initiation and termination End group analysis ( 13 C NMR) shows 50 % ester, 50 % ketone: keto ester, diketone and diester (GC, MS) Two independent initiation and two termination routes: Initiation & termination by methanolysis Hydride initiation Drent, E.; Van Broekhoven, J. A. M.; Doyle, M. J. J. rganomet. Chem. 1991, 417, 235. Bianchini, C.; Meli, A. Coord. Chem. Rev. 2002, 225 (1-2), Drent, E.; Budzelaar,. H. M. Chem. Rev. 1996, 96, 663.

16 End group analysis Drent, E.; Van Broekhoven, J. A. M.; Doyle, M. J. J. rganomet. Chem. 1991, 417, 235.

17 Initiation & termination by methanolysis C C 2 H 4 [d] [d] [d] [d] H [d] H + H 3 C [d] H [d] + Methoxy complex is first formed by methanolysis of palladium precatalyst Initiation by methanolysis gives an ester head, but can give both ester and ketone tails Drent, E.; Budzelaar,. H. M. Chem. Rev. 1996, 96, 663.

18 Hydride initiation C 2 H 4 [d] H [d] C [d] Gives ketone head β-hydrogen elimination from a palladium methoxide Water gas shift reaction Wacker-type oxidation of ethylene Hydrogen activation Alcoholysis (from termination) Drent, E.; Budzelaar,. H. M. Chem. Rev. 1996, 96, 663.

19 Hydride initiation C 2 H 4 [d] H [d] C [d] β-hydrogen elimination Water gas shift reaction Wacker-type oxidation of ethylene Hydrogen activation Alcoholysis [d] [d] + C + [d] + C 2 H 4 + H [d] [d] H + CH H 2 [d] H C 2 H + [d] H + [d] + H 2 [d] H + H + + H [d] H + H 3 C Drent, E.; Budzelaar,. H. M. Chem. Rev. 1996, 96, 663.

20 ropagation [d] C + C [d] C resting state - C [d] + C - C 2 H 4 - C + C 2 H 4 + C - C 2 H 4 - C + C - C 2 H 4 - C + C 2 H 4 + C - C 2 H 4 [d] + C 2 H 4 [d] [d] + C 2 H 4 Rix, F. C.; Brookhart, M.; White,. S. J. Am. Chem. Soc. 1996, 118, Shultz, C. S.; Ledford, J.; DeSimone, J. M.; Brookhart, M. J. Am. Chem. Soc. 2000, 122, [d] = (phen)d 2+

21 Binding affinity of C versus C 2 H 4 [d] K 1 + C 2 H 4 [d] + C C 2 3 K 1 = (4.48 ± 3.14) 10-6, ΔG = (5.12 ± 0.31) kcal/mol K 1 is small; d binds more strongly to C than C 2 H 4 Concentration of palladium ethylene-alkyl complex is kept very low Rix, F. C.; Brookhart, M.; White,. S. J. Am. Chem. Soc. 1996, 118, 4746.

22 [d] C Determination of K 1 S K A [d] + S + C 2 4 [d] S K B [d] + CN + NC S 4 5 [d] NC + C 2 H 4 K C [d] + CN 5 3 Rix, F. C.; Brookhart, M.; White,. S. J. Am. Chem. Soc. 1996, 118, 4746.

23 Binding affinity of C versus C 2 H 4 [d] K 1 + C 2 H 4 [d] + C C 2 3 K at-66 C ΔG (kcal/mol) K A (7.66 ± 3.45) ± 0.2 K B (6.81 ± 0.27) ± 0.02 K C (8.58 ± 1.8) ± 0.09 K 1 (4.48 ± 3.14) ± 0.31 Rix, F. C.; Brookhart, M.; White,. S. J. Am. Chem. Soc. 1996, 118, 4746.

24 Migratory insertion reactions of (phen)d(r)(l) R L ΔG (± 0.1 kcal/mol) (CD 2 Cl 2 ) C (acetone-d 6 ) C CH 2 CH 2 C C C C 2 H Temp. ( C) CCH 2 CH 2 C C 2 H C 2 H CH 2 C 2 H No acceleration from a polar solvent (1-2) Reactions 4-7 insensitive to ethylene concentration (intramolecular) Alkyl migration to ethylene ~ 3 kcal/mol more difficult than for acyl migration (3 & 7) Alkyl-ethylene migratory insertion is disfavored Rix, F. C.; Brookhart, M.; White,. S. J. Am. Chem. Soc. 1996, 118, 4746.

25 Determination of k & ΔG Migratory insertion reactions of (phen)d(r)(l) R L ΔG (± 0.1 kcal/mol) Temp. ( C) (CD 2 Cl 2 ) C (acetone-d 6 ) C CH 2 CH 2 C C C C 2 H CCH 2 CH 2 C C 2 H C 2 H CH 2 C 2 H Rix, F. C.; Brookhart, M.; White,. S. J. Am. Chem. Soc. 1996, 118, 4746.

26 Determination of k & ΔG 1.7 equiv. C [d] [d] C 14 16, 11 % [d] C + [d] 18, 70 % 19, 19 % Rix, F. C.; Brookhart, M.; White,. S. J. Am. Chem. Soc. 1996, 118, 4746.

27 Determination of k & ΔG [d] C + [d] Excess C k = s -1 ΔG = 15.0 kcal/mol [d] C No added C k = s ΔG = 14.9 kcal/mol [d] C 16 Rix, F. C.; Brookhart, M.; White,. S. J. Am. Chem. Soc. 1996, 118, 4746.

28 erfect polymer Double carbonylation is strongly disfavored thermodynamically Multiple ethylene insertions are rare (prob. = ), even with low C concentrations Concentration of alkyl-ethylene complex is very low Exchanges ethylene for C readily Alkyl migration onto ethylene has a higher energy barrier β-coordination of ketone helps ensure C coordinates next Result: perfectly alternating co-polymerization Chen, J. T.; Sen, A. J. Am. Chem. Soc. 1984, 106, Rix, F. C.; Brookhart, M.; White,. S. J. Am. Chem. Soc. 1996, 118, Drent, E.; Budzelaar,. H. M. Chem. Rev. 1996, 96, 663.

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