[((2,6-iPr2C6H3)NC(Me)C(Me)N(2,6-iPr2C6H3))Pd(Et2O)Me]SbF6 | 181707-48-2

• 英文名称: [((2,6-iPr2C6H3)NC(Me)C(Me)N(2,6-iPr2C6H3))Pd(Et2O)Me]SbF6
• CAS: 181707-48-2
• 化学式: C₃₃H₅₃N₂OPd*F₆Sb
• 分子量: 835.957
• InChiKey: OXSXEBMUOFWAQN-OSJKLRTQSA-H

计算性质

• 辛醇/水分配系数(LogP)：
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• 重原子数：
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• 可旋转键数：
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• 环数：
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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

• 作为反应物：
  描述：

  叔丁基乙烯基醚 、 [((2,6-iPr2C6H3)NC(Me)C(Me)N(2,6-iPr2C6H3))Pd(Et2O)Me]SbF6 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
• 作为产物：
  描述：

  silver hexafluoroantimonate 、 乙醚 、 [(2,6-iPrC6H3NC(Me)C(Me)N-2,6-iPrC6H3)Pd(CH3)(Cl)] 以 diethyl ether 为溶剂， 生成 [((2,6-iPr2C6H3)NC(Me)C(Me)N(2,6-iPr2C6H3))Pd(Et2O)Me]SbF6
  参考文献：
  名称：

  乙烯基醚与 (α-二亚胺)PdMe+ 物种反应中的阳离子聚合和插入化学

  摘要：

  (α-二亚胺)PdMe(+) 物种的反应 (1, α-二亚胺 = (2,6-(i)Pr(2)-C(6)H(3))N=CMeCMe=N(2, 6-(i)Pr(2)-C(6)H(3))) 与乙烯基醚 CH(2)=CHOR (2a-g: R = (t)Bu (a), Et (b), SiMe (3) (c), SiMe(2)Ph (d), SiMePh(2) (e), SiPh(3) (f), Ph (g); 2a-g: R = (t)Bu (a) , Et (b), SiMe(3) (c), SiMe(2)Ph (d), SiMePh(2) (e), SiPh(3) (f), Ph (g)) 进行了研究。观察到两种途径。首先，1 引发 2a-c 的阳离子聚合，同时 1 分解为 Pd(0)。该反应通过形成 (α-二亚胺)PdR'(CH(2)=CHOR)(+) pi 复合物（R' = Me 或 CH(2)CHMeOR

  DOI：

  10.1021/ja100491y

文献信息

• Mechanism of the Reaction of Vinyl Chloride with (α-diimine)PdMe⁺ Species
  作者：Stefan M. Kilyanek、Edward J. Stoebenau、Nawaporn Vinayavekhin、Richard F. Jordan

  DOI：10.1021/om1000925

  日期：2010.4.12

  The reaction of vinyl chloride (VC) with (alpha-diimine)PdMe+ species yields (alpha-diimine)PdCl-(propene)(+) Isotope labeling experiments using the deuterium-labeled vinyl chlorides 1-VC-d(1) and Z-VC-d(1) combined with DFT computations establish that this reaction proceeds by 2,1-insertion of VC to produce beta-H agostic (alpha-diimine)Pd(CHClCH2Me)(+), chain-walking isomerization to generate beta-Cl dative (alpha-diimine)Pd(CHMeCH2Cl)(+) and syn beta-Cl elimination. The labeling experiments rule out mechanisms involving initial 1,2-insertion or C-Cl oxidative addition. The computational results and the observation of small amounts of propene-d(2) argue against mechanisms involving 2,1-insertion followed by alpha-Cl elimination and a 1,2 H-shift.