Pd-Promoted Copolymerization of Methallyl and Isoprenyl Ethers and Acetate with α-Olefins

Abstract

1,1-Disubstituted ethylene derivatives with oxygen functionalities, such as methallyl and isoprenyl ethers and acetate, were employed as comonomers with α-olefins catalyzed by Pd–diimine complexes. A mixture of a chloro­(methyl)palladium complex with α-diimine ligand having 2,4,6-trimethylphenyl groups at the coordinated N atoms (I) and Na+B­{C6H3(CF3)2-3,5}4 – catalyzes the copolymerization of 1-decene with methallyl tert-butyl ether (1) at 0 °C to produce copolymers with comonomer content of 9.7 mol %. Methallyl acetate (2) undergoes copolymerization with 1-decene to afford the corresponding copolymers with comonomer content of 1.0 to 3.3 mol %. Nuclear magnetic resonance analyses of the copolymers of 1-decene with 1 and 2 revealed that no significant β-alkoxy or β-acetate elimination takes place during the polymerization and that the insertion mode of the comonomer determines the location of the monomer on either the main chain or the terminal of the copolymer. Related compounds, isoprenyl tert-butyl ether (3), isoprenyl acetate (4), and isoprenyl trimethylsilyl ether (5), undergo copolymerization with 1-decene or 1-hexene to afford the corresponding copolymers with comonomer content of 1.0 to 6.2 mol %. The reaction with a higher concentration of a comonomer results in the formation of polymers with higher comonomer content.

Alkene-Coordinated Palladium(0) Cross-Coupling Precatalysts: Comparing Oxidative Addition and Catalytic Reactivity for Dimethyl Fumarate and Maleic Anhydride Stabilizing Ligands

“…α-Diimine ligands are well-studied in organopalladium chemistry, most notably for Pd(II) olefin polymerization catalysts. − Corresponding Pd(0) complexes with the DAB-variant of α-diimines (derived from glyoxyl) have also been previously studied, , including as precatalysts in Heck coupling, − catalytic alkyne hydrogenation, − methoxycarbonylation of styrene, , and the synthesis of carbohydrate derivatives . Furthermore, several (R 3 P) 2 Pd–DMFU complexes are known, either with simple monophosphines − or with chelating phosphines. − This work provides important structural and synthetic guidance toward candidate Pd(0) precatalysts.…”

Alkene-Coordinated Palladium(0) Cross-Coupling Precatalysts: Comparing Oxidative Addition and Catalytic Reactivity for Dimethyl Fumarate and Maleic Anhydride Stabilizing Ligands

“…α-Diimine ligands are well-studied in organopalladium chemistry, most notably for Pd(II) olefin polymerization catalysts. [43][44][45][46][47][48][49][50][51][52][53][54][55][56][57][58] Corresponding Pd(0) complexes with the DAB-variant of αdiimines (derived from glyoxyl) have also been previously studied, 42,59 including as precatalysts in Heck coupling, [60][61][62][63][64] catalytic alkyne hydrogenation, [65][66][67][68][69] methoxycarbonylation of styrene, 70,71 and the synthesis of carbohydrate derivatives. 72 Furthermore, several (R3P)2Pd-DMFU complexes are known, either with simple monophosphines, [73][74][75][76][77] or with chelating phosphines.…”

Late Transition Metal Complexes for Olefin Copolymerization with Polar Monomers

“…高级 α-烯烃(如 1-己烯)在 6 催化下分别与丙烯酸丁 酯和甲基丙烯酸甲酯共聚 [49] 形成高度支化共聚物(支化 度为 80～122), 极性基团插入率为 3.1%～13.3%, 分子 量为 2.5×10 5 ～3.36×10 5 . 1-癸烯与亚甲基阻隔的 1,1-二取代乙烯基极性单体在 7 催化共聚时得到中等支化度 共聚物 [50] [51] . 在萘 环上引入取代芳基形成夹心结构 Pd 催化剂 12, 轴向位 阻增加减缓链转移速率 [52] ; 乙烯-丙烯酸甲酯共聚物分 子量较 8～11 得以提升(最高为 5.5×10 4 [56] , 27～32 催化乙烯-丙烯酸甲酯共聚 有机化学 综述与进展 活性与类似邻位甲基催化剂相比, 极大降低, 但是共聚 物极性基团插入率得到提高(6%～38%).…”