Late Transition Metal Complex Catalysts for Olefin Polymerization Kotohiro Nomura* This review summarizes the recent developments in the field of olef
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1 Late Transition Metal Complex Catalysts for Olefin Polymerization Kotohiro Nomura* This review summarizes the recent developments in the field of olefin polymerization, especially focuses on the topic by nickel, palladium, iron, cobalt, and ruthenium complex catalysts including the brief summary of this research background. A lot of studies have been explored concerning olefin polymerization by nickel and palladium complex catalysts especially after the discovery of results introduce new possibilities for making new type of olefin-based copolymers by these catalysts. In particular, recent discovery concerning ethylene polymerization by iron and cobalt complexes containing 2,6-bis (imino) pyridine ligand attracted particular attention due to the exceptionally high catalytic activity, and the contents concerning this topic have also been summarized briefly. We also wish to introduce our recent results concerning olefin polymerization by ruthenium and iron complexes-cocatalyst Key words: systems. olefin polymerization, ethylene, propylene, methyl acrylate, nickel, palladium, iron, ruthenium, cobalt, homogeneous catalysts Fig. 1 Typical nickel catalyst for olefin polymerization (W. Keim et al., 1978-)5). * Nara Institute of Science and Technology (NAIST), Graduate School of Materials Science Vol.58 No (23) 293
2 Scheme 1 Insertion mode of a-olefins. Table 1 Ethylene polymerization by nickel catalyst containing P-0 chelate ligand8a). 294 ( 24 )
3 Fig. 3 Explanatory figure for side chain branching. Fig. 2 Genaral formula of nickel and palladium complexes containing Vol.58 No ( 25 ) 295
4 Table 2 Ethylene polymerization by nickel-diimine complexes, (Ar2DABR2)NiBr2, -MAO catalyst11d). -Effect of ligand, reaction temperature, and ethylene pressure- Table 3 Ethylene polymerization by [(2, 6-113r2Ph) DABAn]NiBr2-MAO catalystlle). -Effect of ethylene pressure- Scheme 2 Proposed reaction scheme for ethylene polymerization catalyzed by nickel-diimine complexes-cocatalyst systemlla). 296 ( 26 )
5 Table 4 Polymerization of propylene and 1-hexeneli'd). Scheme 3 1, co-enchainment in a-olefin polymerization. Vol.58 No ( 27 )
6 Table 5 Copolymerization of ethylene and propylene with functionalized vinyl monomers by palladium catalystsild). 298 ( 28 )
7 Scheme 4 Reaction of complex B with acrylatellm). Scheme 5 Insertion of ethylene into complex C. Scheme 6 Proposed reaction scheme for copolymerization of ethylene with methyl acrylatellb'f). Vol.58 No ( 29 ) 299
8 Fig. 4 Nickel complexes reported by Cavell et al23). [Basic Concept for Designing the Catalyst Precursor] 1) Help shield the axial faces and retard chain termination 2) Reduce chain migratory processes (influences branching) by increasing in-plane bulk 3) Enhance catalyst activity by increasing dissociation rate of ancillary PPh3 4) Prevent disproportionation and ligand rearrangement Fig. 6 Nickel and cobalt complexes reported by Laine et al26) Fig. 5 Nickel catalyst reported by Grubbs et aim). Table 6 Polymerization of ethylene by substituted nickel salicylaldimines and phosphine complex catalyst24b). Reaction conditions: catalyst 75 Rmol, Ni(COD)2 (cocatalyst) 150 innol, toluene 90 ml, ethylene psig (ca atm), ice bath was used to control the reaction temperature. Fig. 7 Nickel catalyst reported by Kanemasa et al28). Table 7 Effect of temperature on ethylene polymerization by nickel catalyst24b). Reaction conditions: catalyst (32) 60 gmol, toluene 1000 ml, ethylene 400 psig (ca atm). Fig. 8 Nickel catalyst containing bis(oxazoline)ligands for olefin polymerization29). 300 ( 30 )
9 Table 8 Cobalt catalyzed living polymerization of ethylene35b). Fig. 9 Nickel and palladium complexes containing bis- (pyrazolyl)methane ligand30,31). Scheme 7 Proposed reaction scheme for cobalt catalyzed living polymerization of ethylene35b). Fig. 10 Iron and cobalt complexes for ethylene polymerization32'33). Vol.58 No ( 31 ) 301
10 Table 9 Ethylene polymerization catalyzed by iron and cobalt complexes-cocatalyst systems32b). Table 10 Effect of ligand in ethylene polymerization catalyzed by cobalt complexes. Table 11 Effect of ethylene pressure34b). 302 ( 32 )
11 Scheme 8 Ethylene oligomerization catalyzed by iron complexes33c). Fig. 11 Iron complexes for propylene polymerization336. Table 12 Propylene polymerization catalyzed by iron complexescocatalyst systems336. Scheme 9 Proposed reaction scheme for propylene polymerization catalyzed by iron complexes33c). Vol.58 No ( 33 ) 303
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