Copolymerization of silyl vinyl ethers with olefins by (α-diimine)PdR+

This paper reports that (α-diimine)PdMe+ catalyzes the copolymerization of olefins and silyl vinyl ethers. The reactions of (α-diimine)PdMe+ (α-diimine = (2,6-iPr2-C6H3)N=CMe-CMe=N(2,6-iPr2-C6H3)) with excess vinyl ethers CH2=CHOR (1a-d: R = tBu (a), SiMe3 (b), SiPh3 (c), Ph (d)) in CH2Cl2 at 20 °C afford polymers for 1a (rapidly) and 1b (slowly) but not for 1c or 1d. The structures of poly(1a,b) indicate a cationic polymerization mechanism. The reaction of (α-diimine)PdMe+ with 1-2 equiv of 1a-d proceeds by sequential C=C π-complexation to form (α-diimine)PdMe(CH2=CHOR)+ (2a-d), 1,2 insertion to form (α-diimine)Pd(CH2CHMeOR)+ (3a-d), reversible isomerization to (α-diimine)Pd(CMe2OR)+ (4a-d), β-OR elimination to generate (α-diimine)Pd(OR)(CH2=CHMe)+ (not observed), and allylic C-H activation to yield (α-diimine)Pd(η3-C3H5)+ (5) and ROH. The reaction of (α-diimine)PdMe+ with 1-hexene/1b and 1-hexene/1c mixtures in CH2Cl2 at 20 °C affords copolymers containing up to 20 mol % silyl vinyl ether. The copolymers were purified to be free of any -[CH2CHOSiR3]n- homopolymer. The copolymer structures are similar to that of homopoly(1-hexene) generated under the same conditions. The major comonomer units are CH3CH(OSiR3)CH2-, CH2(OSiR3)CH2- and -CH2CH(OSiR3)CH2-. The 1-hexene/CH2=CHOSiR3 copolymers can be desilylated to give 1-hexene/CH2=CHOH copolymers. The results of control experiments argue against cationic and radical mechanisms for the copolymerization, and an insertion/chain-walking mechanism is proposed. Copyright © 2006 American Chemical Society.