By Ayusman Sen (auth.), Ayusman Sen (eds.)
217 2. COPOLYMERIZATION OF PROPENE OR greater I-ALKENES WITH 218 CARBON MONOXIDE 2. 1. Ligands and polymerization stipulations 218 2. 2. Spiroketal formation 221 2. three. Enantioselectivity 222 2. four. larger I-Alkenes 226 three. COPOLYMERIZATION OF STYRENE OR ITS DERIVATIVES WITH 226 CARBON MONOXIDE four. COPOLYMERIZATION of different OLEANS WITH CARBON MONOXIDE 230 five. uneven TERPOLYMERIZATION OF greater than forms of 232 OLEFINS WITH CARBON MONOXIDE 6. POLYKETONE CONFORMATION 233 7. end 234 bankruptcy eight. Chain Propagation Mechanisms 237 Ayusman Sen 1. advent 237 2. PALLADIUM (II) established platforms 238 three. NICKEL (II) established structures 256 four. RHODIUM (I) established structures 257 five. end 261 bankruptcy nine. Theoretical experiences on Copolymerization of Polar Monomers 265 Peter Margl, Artur Michalak, and Tom Ziegler 1. creation 265 2. COPOLYMERIZATION OF CARBON MONOXIDE WITH ETHYLENE 267 2. 1. Experimental and calculated charges for the insertion methods for 267 copolymerization catalysed via Pd(II) structures. 2. 2. A extra exact examine the effective and unproductive cycles 270 in copolymerization catalysed through Pd(II) complexes. 2. 2. 1. The efficient cycle 270 2. 2. 2. C2H4 misinsertion into an ethylene terminated polyketone 275 chain 2. three. Experimental and calculated charges for the insertion tactics for 277 alternating copolymerization catalyzed via Ni(II) structures three. COPOLYMERIZATION OF OLEFINS WITH POLAR MONOMERS different 280 THAN CO three. 1. most well-liked binding mode of oxygen containing monomers 282 three. 2. most popular binding mode of nitrogen containing monomers 285 three. 3.
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Extra resources for Catalytic Synthesis of Alkene-Carbon Monoxide Copolymers and Cooligomers
W. N. ; Klusener, P. A. ; Stil, H. ; Roobeek, C. F. J. Am. Chern. Soc. 1998, 120,7977. 14 (a) Mulders, J. P. Nelh. Pat. 6604094,1966 (to Shell). (b) Mason, R. F: Winkle, J. L. V. US Pat. 3,400,163, 1968 (10 Shell). ; Pello, D. H. : Eu ... Pat. App!. EP 495,547 A2, 1992 (to Shell). : Pello, D. H. : Suykerbuyk, J. C. J. ; van Gogh, J. B. World. , 5354,1994 (to Shell) (0) Eberhard, M. R. Ph. D. thesis, University of Brislol, 2001. ; Jager, W. W. unpublished results. : Buckler, S. A. J. Am. Chern. Soc.
Mechanistic studies of CO/ethene reactions are discussed in other chapters of this book, but to summarize. two mechanisms are possible, one initiated by a hydride and the other by a methoxy complex. Monomer insertions then occur, as shown in Figure 3-1 and termination is by protonation (usually of a ~-ketoalkylcomplex) or nucleophilic attack of methanol, usually on an acyl complex. As shown in Figure 3-1, these two termination processes can lead to products which have an ethyl group at one end and a methyl ester group at the other.
It is at this stage that hydroformylation and hydroacylation reactions start to diverge (see Figure 2-7). Figure 2-7. Olefin hydroformylation VS. hydroacylation In hydroformylation, hydrogenolysis of the Pd-acyl bond takes place to give the aldehyde product and regenerate the hydride LzPdH+. In hydroacylation, a second olefin molecule coordinates to the Pd-aeyJ, and migratory insertion gives an internally coordinated Pd-alkyl complex (structure A). 22 Stable species of this type have been observed spectroscopically in the studies of olefin insertion in L,Pd-acyl complexes .