((2,6-i-Pr2-C6H3)NCMeCMeN(2,6-i-Pr2-C6H3))Pd(η3-C3H5)(1+) | 791114-74-4

• 英文名称: ((2,6-i-Pr2-C6H3)NCMeCMeN(2,6-i-Pr2-C6H3))Pd(η3-C3H5)(1+)
• 英文别名: [(2,6-(i)Pr2-C6H3)N=CMeCMe=N(2,6-(i)Pr2-C6H3))Pd(allyl)](1+)
• CAS: 791114-74-4
• 化学式: C₃₁H₄₅N₂Pd
• 分子量: 552.132
• InChiKey: IKWCSBVHQCLGGL-HEVKTJNJSA-N

计算性质

• 辛醇/水分配系数(LogP)：
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• 重原子数：
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• sp3杂化的碳原子比例：
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• 拓扑面积：
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• 氢给体数：
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• 氢受体数：
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反应信息

• 作为产物：
  描述：

  叔丁基乙烯基醚 、 [(2,6-iPrC6H3NC(Me)C(Me)N-2,6-iPrC6H3)Pd(CH3)(Cl)] 在 (Li(Et₂O)2.8)B(C₆F₅)4 作用下， 以 二氯甲烷 为溶剂， 生成 ((2,6-i-Pr2-C6H3)NCMeCMeN(2,6-i-Pr2-C6H3))Pd(η3-C3H5)(1+)
  参考文献：
  名称：

  Copolymerization of Silyl Vinyl Ethers with Olefins by (α-diimine)PdR⁺

  摘要：

  This paper reports that (alpha-diimine)PdMe+ catalyzes the copolymerization of olefins and silyl vinyl ethers. The reactions of (alpha-diimine)PdMe+ (alpha-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 degrees 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 (alpha-diimine)PdMe+ with 1-2 equiv of 1a-d proceeds by sequential C=C pi-complexation to form (alpha-diimine)PdMe(CH2=CHOR)+ (2a-d), 1,2 insertion to form (alpha-diimine)Pd(CH2CHMeOR)+ (3a-d), reversible isomerization to (alpha-diimine)Pd(CMe2OR)+ (4a-d), beta-OR elimination to generate (alpha-diimine)Pd(OR)(CH2=CHMe)+ (not observed), and allylic C-H activation to yield (alpha-diimine)Pd(eta3-C3H5)+ (5) and ROH. The reaction of (alpha-diimine)PdMe+ with 1-hexene/1b and 1-hexene/1c mixtures in CH2Cl2 at 20 degrees 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.

  DOI：

  10.1021/ja064398w

文献信息

• Chen, Changle; Luo, Shuji; Jordan, Richard F., Journal of the American Chemical Society, 2008, vol. 130, p. 12892 - 12893
  作者：Chen, Changle、Luo, Shuji、Jordan, Richard F.

  DOI：——

  日期：——