(η2-fumaronitrile)(Ph2PC6H4CHNC6H4OMe-4)palladium(0) | 212317-60-7

• 英文名称: (η2-fumaronitrile)(Ph2PC6H4CHNC6H4OMe-4)palladium(0)
• CAS: 212317-60-7
• 化学式: C₃₀H₂₄N₃OPPd
• 分子量: 579.934
• InChiKey: ZWDLQLBLZMSDAM-UYAPIEALSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  None
• 重原子数：
  None
• 可旋转键数：
  None
• 环数：
  None
• 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

• 作为反应物：
  描述：

  (η2-fumaronitrile)(Ph2PC6H4CHNC6H4OMe-4)palladium(0) 、 Ph2PC6H4CH=N-4-MeOC6H4 以 二氯甲烷 为溶剂， 以84%的产率得到Pd(η(2)-fumaronitrile)(o-Ph2PC6H4CH=NC6H4OMe-4)2
  参考文献：
  名称：

  钯（0）-烯烃配合亚氨基膦配体的制备及反应

  摘要：

  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

  DOI：

  10.1016/s0022-328x(98)00472-0
• 作为产物：
  描述：

  Ph2PC6H4CH=N-4-MeOC6H4 在 diethylamine 作用下， 以 甲醇 、 二氯甲烷 、 氯仿 为溶剂， 生成 (η2-fumaronitrile)(Ph2PC6H4CHNC6H4OMe-4)palladium(0)
  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

• Mechanistic study on the coupling reaction of aryl bromides with arylboronic acids catalyzed by (iminophosphine)palladium(0) complexes. Detection of a palladium(ii) intermediate with a coordinated boron anion
  作者：Bruno Crociani、Simonetta Antonaroli、Alessia Marini、Ugo Matteoli、Alberto Scrivanti

  DOI：10.1039/b514405a

  日期：——

  4-R2C6H4B(OH)2 (R2= H, Me, OMe, Cl) to give [Pd(eta2-ol)(P-N)] and the corresponding biaryl through transmetallation and fast reductive elimination. The transmetallation proceeds via a palladium(II) intermediate with an O-bonded boron anion, the formation of which is markedly retarded by increasing the bulkiness of R. The intermediate was isolated for R = CHMe2, R1 = CF3 and R2= H. The boron anion is formulated

  配合物[Pd（eta2-dmfu）（PN）] [PN = 2-（PPh2）C6H4-1-CH = NR，R = C（6）H（4）OMe-4; CHMe2; Me2-2,6; C6H3（CHMe2）-2,6]与过量的Br R1-4（R1 = CF3; Me）反应，生成取决于R [ OMe-4]的不同速率的氧化加成产物[PdBr（ R1-4）（PN）] > （CHMe2）-2,6> CHMe2大约为 Me2-2,6]和R1（ >> Me）。在K2CO3和活化烯烃（ol = dmfu，fn）的存在下，后一种化合物与过量的4-R2 B（OH）2（R2 = H，Me，OMe，Cl）反应生成[Pd（eta2-ol） ）（PN）]和相应的联芳基通过金属转移和快速还原消除。通过带有O键键合的硼阴离子的钯（II）中间体进行金属转移反应，该中间体的形成因R的
• Kinetic Studies of the Oxidative Addition and Transmetallation Steps Involved in the Cross‐Coupling of Alkynyl Stannanes with Aryl Iodides Catalysed by η ² ‐(Dimethyl fumarate)(iminophosphane)palladium(0) Complexes
  作者：Bruno Crociani、Simonetta Antonaroli、Luciano Canovese、Paolo Uguagliati、Fabiano Visentin

  DOI：10.1002/ejic.200300376

  日期：2004.2

  dmfu analogue 1a. The kinetics of the oxidative addition of ArI (Ar = C6H4CF3-4) to 1a and 2a lead to the products [PdI(Ar)(P-N)] (1c, 2c) and obey the rate law, k(obs) = k(1A) + k(2A)[ArI]. The k(1A) step involves oxidative addition to a reactive species [Pd(solvent)(P-N)] formed from dmfu dissociation. The k2A step is better interpreted in terms of oxidative addition to a species [Pd(eta(2) -dmfu)

  配合物 [Pd(eta(2)-dmfu)(PN)] dmfu = 富马酸二甲酯；PN = 2-(PPh2)C6H4-1-CH=NR, R = OMe-4 (1a), CHMe2 (2a), Me2-2,6 (3a), C6H3(CHMe2)(2)-2,6 ( 4a)} 在溶液中经历动态过程，包括 PN 配体位点交换，通过 Pd-N 键在较低能量下的初始断裂和在较高能量下的烯烃离解-缔合。根据烯烃置换的平衡常数值，复合物 [Pd(eta(2)-fn)(PN)]（fn = 富马腈，1b）比其 dmfu 类似物 1a 具有更高的热力学稳定性。ArI (Ar = CF3-4) 氧化加成到 1a 和 2a 的动力学导致产物 [PdI(Ar)(PN)] (1c, 2c) 并遵守速率定律，k(obs) = k( 1A) + k(2A)[ArI]。k(1A) 步骤涉及对由 dmfu
• Mechanistic study on the cross-coupling of alkynyl stannanes with aryl iodides catalyzed by η²-(dimethyl fumarate)palladium(<scp>0</scp>) complexes with iminophosphine ligands
  作者：Bruno Crociani、Simonetta Antonaroli、Valentina Beghetto、Ugo Matteoli、Alberto Scrivanti

  DOI：10.1039/b300020f

  日期：——

  The reactions of [Pd(η2-dmfu)(P–N)] [dmfu = dimethyl fumarate; P–N = 2-(PPh2)C6H4-1-CHNR, R = C6H4OMe-4 (1a), CHMe2 (2a)] and [Pd(η2-dmfu)(P–N)2] with IC6H4CF3-4, ISnBu3 and PhCCSnBu3 have been studied under pseudo-first-order conditions. The oxidative addition of IC6H4CF3-4 yields [PdI(C6H4CF3-4)(P–N)] (1b or 2b). No reaction takes place with PhCCSnBu3 and also with ISnBu3 in the presence of an excess of PhCCSnBu3. In the presence of fumaronitrile (fn), 1b and 2b undergo transmetalation by PhCCSnBu3 followed by fast reductive elimination to yield [Pd(η2-fn)(P–N)]. The same reaction sequence occurs for the system [PdI(C6H4CF3-4)(P–N)]/P–N (1 ∶ 1 molar ratio) to give [Pd(η2-fn)(P–N)2]. The palladium(0) complexes are active catalysts in the cross-coupling of PhCCSnBu3 with aryl iodides ArI (Ar = C6H4CF3-4, Ph). The catalytic efficiency depends on the complex: [Pd(η2-dmfu)(P–N)2] > [Pd(η2-dmfu)(P–N)], and on the substituent R: C6H4OMe-4 > CHMe2. The reactivity and spectroscopic data suggest a catalytic cycle involving initial oxidative addition of ArI to a palladium(0) species, followed by transmetalation of the product and by fast reductive elimination to regenerate the starting palladium(0) compound. For [Pd(η2-dmfu)(P–N)] as catalyst, the oxidative addition is the rate-determining step, while for [Pd(η2-dmfu)(P–N)2] the oxidative addition and the transmetalation steps occur at comparable rate.

  在伪一阶条件下研究了[Pd(δ-2-dmfu)(PâN)][dmfu = 富马酸二甲酯；PâN = 2-(PPh2)C6H4-1-CHNR, R = OMe-4 (1a), CHMe2 (2a)] 和[Pd(δ-2-dmfu)(PâN)2]与 I CF3-4、ISnBu3 和 PhCCSnBu3 的反应。I CF3-4 的氧化加成反应生成了[PdI( CF3-4)(PâN)]（1b 或 2b）。与 PhCCSnBu3 不发生反应，与 ISnBu3 在过量 PhCCSnBu3 的存在下也不发生反应。在富马腈（fn）存在的情况下，1b 和 2b 通过 PhCCSnBu3 发生反金属反应，然后快速还原消除，生成 [Pd(δ-2-fn)(PâN)]。同样的反应顺序也发生在[PdI( CF3-4)(PâN)]/PâN（1ⶠ1 摩尔比）体系中，生成[Pd(δ-2-fn)(PâN)2]。钯（0）配合物是 PhCCSnBu3 与芳基碘化物 ArI（Ar = CF3-4，Ph）发生交叉偶联反应的活性催化剂。催化效率取决于配合物：[Pd(δ-2-dmfu)(PâN)2] > [Pd(δ-2-dmfu)(PâN)]，以及取代基 R： OMe-4 > CHMe2。反应活性和光谱数据表明，催化循环涉及 ArI 与钯(0)物种的初始氧化加成，然后是产物的反金属化和快速还原消除以再生起始钯(0)化合物。对于作为催化剂的[Pd(δ-2-dmfu)(PâN)]来说，氧化加成是决定速率的步骤，而对于[Pd(δ-2-dmfu)(PâN)2]来说，氧化加成和脱金属步骤的速率相当。
• 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.