Synthesis and Reactivity of Palladium(II) Alkyl Complexes that Contain Phosphine-cyclopentanesulfonate Ligands
Synthesis and Reactivity of Palladium(II) Alkyl Complexes that Contain Phosphine-cyclopentanesulfonate Ligands
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DOI：
10.1021/acs.organomet.7b00572
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发表时间：
2017-08
期刊：
影响因子：
2.8
通讯作者：
R. Black;R. F. Jordan
中科院分区：
文献类型：
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作者：
R. Black;R. F. Jordan
合成了膦-环戊磺酸盐前配体Li/K[2-PPh2-环戊烷磺酸](Li/K[2a])、Li/K[2-P(2-OMe-Ph)2-环戊烷磺酸](Li/K[2b])和H[2b]，以及相应的Pd(II)烷基配合物(κ2-P，O-2a)PdMe(吡啶)(3a)和(κ2-P，O-2b)PdMe(吡啶)(3b)。用B(C6F5)3从3b中提取吡啶，合成了磺酸桥联的无碱二聚体{(2b)PdMe}2(4b)。B(C6F5)3与磺酸氧键的配位无碱二聚体[{2b·B(C6F5)3}PdMe]2(5b)是通过每钯加1当量的B(C6F5)3到4b或加2当量的B(C6F5)3到3b得到的。化合物3b、4b和5b将低活性(在250磅/平方英寸和80°C下高达210公斤摩尔-1小时-1)的乙烯聚合为线性聚乙烯(Mn=1950-5250 Da)，主要是内部烯烃放置。以−CH2CH(CO2Me)CH2-(80%)在链上的形式引入3b和4b，使乙烯与丙烯酸甲酯共聚，得到含丙烯酸甲酯11.7mol%的线型共聚物。
The synthesis of the phosphine-cyclopentanesulfonate pro-ligands Li/K[2-PPh2-cyclopentanesulfonate] (Li/K[2a]), Li/K[2-P(2-OMe-Ph)2-cyclopentanesulfonate] (Li/K[2b]), and H[2b], and the corresponding Pd(II) alkyl complexes (κ2-P,O-2a)PdMe(pyridine) (3a) and (κ2-P,O-2b)PdMe(pyridine) (3b) is described. The sulfonate-bridged base-free dimer {(2b)PdMe}2 (4b) was synthesized by abstraction of pyridine from 3b using B(C6F5)3. The borane-coordinated base-free dimer [{2b·B(C6F5)3}PdMe]2 (5b), in which B(C6F5)3 binds to a sulfonate oxygen, was prepared by addition of 1 equiv of B(C6F5)3 per Pd to 4b or addition of 2 equiv of B(C6F5)3 to 3b. Compounds 3b, 4b, and 5b polymerize ethylene with low activity (up to 210 kg mol–1 h–1 at 250 psi and 80 °C) to linear polyethylene (Mn = 1950–5250 Da) with predominantly internal olefin placements. 3b and 4b copolymerize ethylene with methyl acrylate to linear copolymers that contain up to 11.7 mol % methyl acrylate, which is incorporated as −CH2CH(CO2Me)CH2– (80%) in-chain u...