Electrophilic Binuclear Methylpalladium(II) Complexes: Copolymerization of Alkenes and Carbon Monoxide
详细信息 查看全文
- 作者：Cliff R. Baar ; Michael C. Jennings ; and Richard J. Puddephatt
- 刊名：Organometallics
- 出版年：2001
- 出版时间：August 6, 2001
- 年：2001
- 卷：20
- 期：16
- 页码：3459 - 3465
- 全文大小：109K
- 年卷期：v.20,no.16(August 6, 2001)
- ISSN：1520-6041
文摘
Reaction of [PdMe2(
-pyd)]2 (pyd = pyridazine) with the bis(bidentate) ligands R,R/S,S-trans-1,2-C6H10(N=CH-2-C5H4N)2, 1, or C2H4(N=CH-2-C5H4N)2, 2, gave the binucleardimethylpalladium(II) complexes R,R/S/S-trans-1,2-[C6H10{N=CH-2-C5H4N(PdMe2)}2], 3,or [C2H4{N=CH-2-C5H4N(PdMe2)}2], 4, respectively. Complex 3 is C2-symmetric. Reactionof 3 or 4 with 2 equiv of [H(OEt2)2][BAr'4], Ar' = 3,5-(CF3)2C6H3, in acetonitrile, gave methaneand the electrophilic binuclear complexes R,R/S,S-trans-1,2-[C6H10{N=CH-2-C5H4N(PdMe(NCMe))}2][BAr'4]2, 5, and [C2H4{N=CH-2-C5H4N(PdMe(NCMe))}2][BAr'4]2, 6, by methylpalladium bond protonolysis. Complexes 5 and 6 could be converted to the acyl complexes R,R/S,S-trans-1,2-[C6H10{N=CH-2-C5H4N(Pd(NCMe)(COMe))}2][BAr'4]2, 7, and [C2H4{N=CH-2-C5H4N(Pd(NCMe)(COMe))}2][BAr'4]2, 8, in the presence of carbon monoxide and were foundto be catalyst precursors for the copolymerization of styrene or 4-methylstyrene with carbonmonoxide. Copolymerization reactions catalyzed with optically pure R,R-5* and achiral 6were carried out at room temperature and pressure to give polyketones, whose chiralmicrostructures are described.
-pyd)]2 (pyd = pyridazine) with the bis(bidentate) ligands R,R/S,S-trans-1,2-C6H10(N=CH-2-C5H4N)2, 1, or C2H4(N=CH-2-C5H4N)2, 2, gave the binucleardimethylpalladium(II) complexes R,R/S/S-trans-1,2-[C6H10{N=CH-2-C5H4N(PdMe2)}2], 3,or [C2H4{N=CH-2-C5H4N(PdMe2)}2], 4, respectively. Complex 3 is C2-symmetric. Reactionof 3 or 4 with 2 equiv of [H(OEt2)2][BAr'4], Ar' = 3,5-(CF3)2C6H3, in acetonitrile, gave methaneand the electrophilic binuclear complexes R,R/S,S-trans-1,2-[C6H10{N=CH-2-C5H4N(PdMe(NCMe))}2][BAr'4]2, 5, and [C2H4{N=CH-2-C5H4N(PdMe(NCMe))}2][BAr'4]2, 6, by methylpalladium bond protonolysis. Complexes 5 and 6 could be converted to the acyl complexes R,R/S,S-trans-1,2-[C6H10{N=CH-2-C5H4N(Pd(NCMe)(COMe))}2][BAr'4]2, 7, and [C2H4{N=CH-2-C5H4N(Pd(NCMe)(COMe))}2][BAr'4]2, 8, in the presence of carbon monoxide and were foundto be catalyst precursors for the copolymerization of styrene or 4-methylstyrene with carbonmonoxide. Copolymerization reactions catalyzed with optically pure R,R-5* and achiral 6were carried out at room temperature and pressure to give polyketones, whose chiralmicrostructures are described.