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Ethylene Oligomerization and Polymerization by Palladium(II) Methyl Complexes Supported by Phosphines Bearing a Perchlorinated 10-Vertex closo-Carborane Anion Substituent
Organometallics ( IF 2.5 ) Pub Date : 2018-12-13 , DOI: 10.1021/acs.organomet.8b00772
Jack F. Kleinsasser 1 , Erik D. Reinhart 2 , Jess Estrada 1 , Richard F. Jordan 2 , Vincent Lavallo 1
Affiliation  

The synthesis and ethylene reactivity of the zwitterionic Pd methyl complexes (κ2-P,Cl-PR2CB9Cl9)PdMe(THF) (7, R = iPr; 8, R = Ph) and (κ2-P,O-P(o-OMe-Ph)2CB9Cl9)PdMe(THF) (9), which contain the first phosphines appended with anionic 10-vertex perchlorinated closo-carboranes, are described. Complexes 7 and 8 oligomerize ethylene (23 °C, 2 atm) to a Schulz–Flory distribution of C4–C10 olefins with TOFs of ca. 8000 and 1800 t.o./h, respectively. 8 is ca. 4 times more active than the analogous (κ2-P,F-ortho-PPh2C6H4BF3)PdMe(L) (L = pyridine or collidine) system reported by Jordan and Piers, which produces butenes. Complex 9 reacts with ethylene to yield polyethylene wax (Mn ca. 1000, Đ ca. 1.5) that is similar to commercial Fischer–Tropsch waxes. The activities of 79 are independent of ethylene pressure and the presence of B(C6F5)3, suggesting that the catalyst resting state is the corresponding (PR2CB9Cl9)PdR(H2C═CH2) adduct. The molecular weights of the oligomer/polymer products are independent of ethylene pressure, which is consistent with an associative chain transfer mechanism. Reaction of 9 with ethylene generates the corresponding ethylene complex (κ2-P,O-P(o-OMe-Ph)2CB9Cl9)PdMe(H2C═CH2), which inserts ethylene at −20 °C with a barrier (ΔGinsertion) of 18.1 kcal/mol.

中文翻译:

乙烯齐聚和聚合由钯(II)配合物的甲基支持膦轴承一个全氯代10顶点闭合碳-Carborane阴离子取代基

所述两性离子的Pd甲基络合物的合成和乙烯的反应(κ 2 - P-PR 2 CB 99)PDME(THF)(7,R =镨; 8,R = PH)和(κ 2 - Pø -P(Ô -OMe-PH)2 CB 99)PDME(THF)(9),其中包含与阴离子10顶点全氯化所附第一膦闭合碳-carboranes,进行说明。配合物78将乙烯(23°C,2 atm)低聚为C 4 –C 10烯烃的舒尔茨-弗洛里分布,TOF约为20。分别为8000 to / h和1800 to / h。大约是8。4倍,比类似的多种活性(κ 2 - P˚F --PPh 2 ç 6 ħ 4 BF 3)PDME(L)(L =吡啶或可力丁)系统报告约旦和码头,它产生丁烯。配合物9与乙烯反应生成聚乙烯蜡(M n约1000,Đ约1.5),类似于商业费托蜡。的活动7 - 9是独立的乙烯压力和B(C的存在的6 ˚F 53,这表明催化剂静止状态是相应的(PR 2 CB 99)PDR(H 2 C = CH 2)加合物。低聚物/聚合物产物的分子量与乙烯压力无关,这与缔合链转移机理是一致的。的反应9与乙烯产生对应的乙烯复合物(κ 2 - Pö -P(Ô -OMe-PH)2 CB 9CL 9)PDME(H 2 C = CH 2),该插入件乙烯在-20℃下用阻挡(Δ ģ 插入的18.1千卡/摩尔)。
更新日期:2018-12-14
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