Pd(η(2)-fumaronitrile)(o-Ph2PC6H4CH=N-t-Bu) | 212317-65-2

• 英文名称: Pd(η(2)-fumaronitrile)(o-Ph2PC6H4CH=N-t-Bu)
• CAS: 212317-65-2
• 化学式: C₂₇H₂₆N₃PPd
• 分子量: 529.917
• InChiKey: HZAKLVGRRPUONI-GVWFRYQLSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  None
• 重原子数：
  None
• 可旋转键数：
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• 环数：
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• sp3杂化的碳原子比例：
  None
• 拓扑面积：
  None
• 氢给体数：
  None
• 氢受体数：
  None

反应信息

• 作为产物：
  描述：

  N-(2'-diphenylphosphinobenzylidene)-tert-butylamine 在 piperidine 作用下， 以 甲醇 、 二氯甲烷 、 氯仿 为溶剂， 生成 Pd(η(2)-fumaronitrile)(o-Ph2PC6H4CH=N-t-Bu)
  参考文献：
  名称：

  阳离子烯丙基钯（II）与亚氨基膦配体的溶液行为和X射线结构。仲胺进行烯丙基胺化反应的动力学和机理

  摘要：

  该阳离子配合物的溶液行为[加入Pd（η 3 -烯丙基）（P-N）] +（P-N = Ö - （PPH 2）C 6 H ^ 4 CH NR（R = C 6 H ^ 4 OME-4， Me，CMe 3（（R）-bornyl）;烯丙基=丙烯基（1a - 4a）和3-甲基-2-丁烯基（1b - 4b））本质上由三个动力学过程组成：（i）非常快的构象变化该P-N螯合环，其中以上和P的Pd-N配位平面下方移动时，（ⅱ）比较快的η 3 -η 1 -η 3互这带来一个SYN -抗只为烯丙基质子交换顺磷; （ⅲ）的η较慢表观旋转3 -烯丙基配体围绕其键轴。对于图1B - 3B，两种几何异构体观察到，具有烯丙基CME的主要一个2组反式磷。含有手性（R）-冰片基的配合物4a和4b分别与两种和四种非对映异构体一起存在于溶液中。的X射线结构分析图4b（CLO 4）显示在晶胞中存在两个非对映异构分子，它们均具有扭曲的

  DOI：

  10.1021/om980858l

文献信息

• Preparation and reactions of palladium(0)–olefin complexes with iminophosphine ligands
  作者：Simonetta Antonaroli、Bruno Crociani

  DOI：10.1016/s0022-328x(98)00472-0

  日期：1998.6

  conveniently obtained via olefin substitution from [Pd(η2-dmf)o-(Ph2P)–C6H4–CHNC6H4OMe-4}]. The α-diimine ligand of [Pd(η2-fn)(py-2-CHNC6H4OMe-4)] is quantitatively displaced by the appropriate iminophosphine to give [Pd(η2-fn)o-(Ph2P)–C6H4–CHNC6H4OMe-4}]. The new zerovalent complexes with P–N ligands are characterized by multinuclear NMR spectroscopy. In solution, olefin rotation or olefin exchange are

  的配合物[加入Pd（η 2 -醇） ø - （PH 2 P）-C 6 H ^ 4 -CHNR}] [醇，富马酸二甲酯（DMF），1,4-萘醌（NQ），富马腈（FN）; R = C ^ 6 ħ 4 OME-4，CME 3中，Me，冰片基]可以以良好的产率从烯丙基衍生物[Pd中的反应来制备（η 3 -C 3 H ^ 5） ø - （PH 2 P） - C 6 H 4 –CHNR}] BF 4在活化烯烃醇的存在下用过量的NHEt 2。络合物[加入Pd（η 2 -毫安） ø - （PH 2 P）-C 6 H ^ 4 -CHNC 6 ħ 4 OME-4}]（毫安，马来酸酐）通过从烯烃置换更方便地得到[加入Pd（η 2 - DMF） ø - （PH 2 P）-C 6 H ^ 4 -CHNC 6 ħ 4 OME-4}]。[Pd（η）的α-二亚胺配体2 - FN）（PY-2-CHNC 6
• Kinetics and mechanism of regioselective amination of the 1-phenylallyl group in cationic palladium(II) complexes bearing bidentate ligands
  作者：Bruno Crociani、Simonetta Antonaroli、Luciano Canovese、Fabiano Visentin、Paolo Uguagliati

  DOI：10.1016/s0020-1693(01)00333-4

  日期：2001.4

  The complexes [Pd(eta (3)-1-PhC3H4)(L-L')(=) [L-L' = 2-(PPh2)C6H4-1-CH=N (R = Me (1a), i-Pr (1b), t-Bu (1c), (R)-bornyl (1d), C6H4OMe-4 (1e), C6H3Me2-2,6 (1f), C6H3(i-Pr)(2)-2,6 (1g)), 6-MeC5H3N-2-CH=NC6H4OMe-4 (2a), C5H4N-2-CH=N-t-Bu (2b) and C5H4N-2-CH2S-t-Bu (3a)] are generally present in solution as two geometrical isomers, the relative abundance of which depends essentially on the steric requirements of the L-L' ligand. In the presence of fumaronitrile the cationic complexes undergo a regioselective amination by secondary amines HY at the CH, allyl terminus, yielding [Pd(eta (2)-fn)(L-L')] and the allylamines (E)-PhCH=CHCH2Y. Under pseudo-first-order conditions the amination rates (k(obs)) are found to depend on the k(2)[HY] term for 2a and 3a, and on the sum k(2)[HY] + k(3)[HY](2) for the other complexes. The second-order term k(2) is related to direct nucleophilic attack on the CH, allyl terminus of the substrate whereas the third-order term k(3) is ascribed to parallel attack by a further HY molecule on the intermediate [Pd(1-PhC3H4)(L-L')(HY)](+). The k(2) values depend on the steric and electronic properties of both the amine HY and the ligand L-L'. For complexes 1a-1g, the relatively higher k(2) values and their increase with increasing steric crowding at the nitrogen-bonded carbon of substituent R are interpreted in terms of a greater reactivity of the isomer with the CH2 allyl terminus trans to phosphorus and cis to the NR group. The high amination rate of 2a, as compared with that of 2b, is related to substantial steric interaction of the CH2 allyl terminus with the 6-Me pyridine group in close proximity in the predominant isomer. (C) 2001 Elsevier Science B.V. All rights reserved.