[Pd(η2-fumaronitrile)(NC5H4(CH=NC6H4OMe-4)-2)] | 132764-00-2

• 英文名称: [Pd(η2-fumaronitrile)(NC5H4(CH=NC6H4OMe-4)-2)]
• CAS: 132764-00-2
• 化学式: C₁₇H₁₄N₄OPd
• 分子量: 396.744
• InChiKey: RMPIBALFYPOZPY-OKTDMCONSA-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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• 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

• 作为产物：
  描述：

  反丁烯二腈 、 以 二氯甲烷 为溶剂， 以94%的产率得到[Pd(η2-fumaronitrile)(NC5H4(CH=NC6H4OMe-4)-2)]
  参考文献：
  名称：

  含2-吡啶基甲亚胺配体的零价钯络合物的烯烃取代平衡和速率

  摘要：

  平衡常数ķ Ë已经针对钯烯烃susbtitution确定（0）α-二亚胺烯烃（醇）配合物[钯（η 2 -醇）（L-L）]通过醇'在氯仿[L-L = 2- NC 5 H 4 CH NC 6 H 4 OMe-4; ol =富马酸二甲酯（dmf），ol'=丙烯腈（an），1-氯-1-氰基乙烯，1,4-萘醌（nq），四甲基乙撑羧酸（tmetc），富马腈（fn）或马来酸酐（ma）; ol = nq，ol'= tmetc，fn或ma]。除了当ol = dmf，nq，ol'= tm等时，取代平衡很快建立，并通过UV / VIS和1 H NMR光谱进行了研究。该ķ Ë值随进入的活化烯烃的电子亲和力的增加而增加。通过UV / VIS技术在各种温度下监测缓慢接近平衡的动力学。当ol = dmf，ol'= tmetc时，仅可以以足够的精度测量正向步阶的二阶速率常数k 2，而对于ol = nq，ol'= tmetc则正向步阶的常数（k

  DOI：

  10.1039/dt9960001921

文献信息

• Equilibrium studies of α-diimine displacement in cationic allylpalladium(<scp>II</scp>) complexes by monodentate N-donors and the mechanism of allyl amination by triethylamine and pyridine
  作者：Luciano Canovese、Fabiano Visentin、Paolo Uguagliati、Francesca Di Bianca、Simonetta Antonaroli、Bruno Crociani

  DOI：10.1039/dt9940003113

  日期：——

  In the cationic complexes [Pd(eta3-allyl)(L-L)]ClO4 [L-L = 1,2-bis(imino)ethanes or 2-(iminomethyl)-pyridines] the chelated alpha-diimine was rapidly and reversibly displaced by secondary amines (N-methylaniline, morpholine or piperidine), triethylamine and 4-substituted pyridines. The observed equilibrium constants K(e) increased with increasing basicity and decreasing steric requirements of the entering N-donor. They strongly depend on the alpha-diimine and decrease in the order RN=CHCH=NR much-greater-than RN=C(Me)C(Me)=NR almost-equal-to NC5H4(CH=NR)-2 (R = C6H4OMe-4). The cationic complex [Pd(eta3-C3H5)NC5H4(CH=NC6H4OMe-4)-2}]+ underwent a slow allyl amination by triethylamine or pyridine (L') in the presence of fumaronitrile (fn), yielding [Pd(eta2-fn)NC5H4(CH=NC6H4OMe-4)-2}] and Et3N+CH2CH=CH2 or C5H5N+CH2CH=CH2. Kinetic studies showed that the pseudo-first-order rate constants for amination (k(obs)) are given by k(obs) = k2[L'], suggesting a direct bimolecular attack of L' on the eta3-allyl ligand. Amination hardly proceeds in the presence of the less-activated olefin dimethyl fumarate (dmf). The pi-accepting properties of the olefinic ligands play an important role also in the reaction of Et3N+CH2CH=CH2 or C5H5N+CH2CH=CH2 with [Pd(eta2-olefin)NC5H4(CH=NC6H4OMe-4)-2}] (olefin = fn or dmf), i.e. the reverse of the amination reaction.