2,3,4,5-tetrakis(carbomethoxy)palladacyclopentadiene(2,2'-bipyridine) | 35916-22-4

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡啶及其衍生物
• 英文名称: 2,3,4,5-tetrakis(carbomethoxy)palladacyclopentadiene(2,2'-bipyridine)
• 英文别名: [(2,2'-bipyridyl)Pd(CCOOMe)4]；[Pd(2,2'-bipyridine)(C4(COOMe)4)]；[Pd(BiPy)(C4(COOMe)4)]；[Pd(C4(COOMe)4)(2,2'-bipyridyl)]；[Pd(C4(COOMe)4)(bipy)]；palladium(2+);2-pyridin-2-ylpyridine;tetramethyl buta-1,3-diene-1,2,3,4-tetracarboxylate
• CAS: 35916-22-4
• 化学式: C₂₂H₂₀N₂O₈Pd
• 分子量: 546.829
• InChiKey: NPLNCDAURSMLQY-UHFFFAOYSA-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：

  2,3,4,5-tetrakis(carbomethoxy)palladacyclopentadiene(2,2'-bipyridine) 、 溴 以 二氯甲烷 为溶剂， 以92%的产率得到(E,E)-(1,2,3,4-tetrakis(carbomethoxy)-4-bromo-1,3-butadienyl)(2,2'-bipyridine)palladium(II) bromide
  参考文献：
  名称：

  分子卤素与含双氮配体的Palladacyclopentadienes的立体定向反应，通过钯（IV）中间体生成1,4-二卤代-1,3-二烯

  摘要：

  合成和计算研究涉及到含有双齿氮配体的戊四环戊二烯对二卤素的反应性。2,3,4,5-四（碳甲氧基）四环环戊二烯（NN）（1a - c ; NN = 9,10-双（苯基亚氨基）-9,10-二氢菲（phenyl-bip，a），bis（p -tolylimino）ac（（p - tolyl）-bian，b），2,2'-联吡啶（bpy，c））与分子二卤素反应生成（E，E）-1,4-dihalo-1,2， 3,4-四（碳甲氧基）-1,3-丁二烯和PdX 2（NN）（X = Cl，Br，I）。palladacycles 1a，b在203−208 K处与溴反应，得到钯（IV）物种反式，顺式，顺式-（（E，E）-2,3,4,5-四（碳甲氧基）四环戊二烯二溴化物（NN）（3av和3bv，分别通过低温1 H NMR观察到。在243 K以上发生还原消除，二价化合物（E，E）-{1,2,3,4-四（羰甲氧基）-4-卤代1

  DOI：

  10.1021/om020586t
• 作为产物：
  描述：

  [Pd(2,2'-bipyridyl)(η2-dimethylfumarate)] 、 丁炔二酸二甲酯 以 氯仿 为溶剂， 生成 2,3,4,5-tetrakis(carbomethoxy)palladacyclopentadiene(2,2'-bipyridine)
  参考文献：
  名称：

  Mechanistic and Kinetic Investigation on the Formation of Palladacyclopentadiene Complexes. A Novel Interpretation Involving a Bimolecular Self-Reaction of a Monoalkyne Intermediate

  摘要：

  The stoichiometric reaction between the complex [Pd(eta(2)-dmfu)(BiPy)] (dmfu = dimethylfumarate; BiPy = 2,2'-bipyridine) and the deactivated alkynes dmbd (dimethyl-2-butynedioate) and pna (methyl (4-nitrophenyl)propynoate), providing the respective palladacyclopentadienes, was investigated. The mechanism leading to the palladacyclopentadiene derivative involves a bimolecular self-rearrangement of the monoalkyne intermediate [Pd(eta(2)-alk)(BiPy)] (alk = dmbd, pna), followed by the customary attack of the free alkyne on the intermediate [Pd(eta(2)-alk)(BiPy)] itself and on the elusive and highly reactive "naked palladium" [Pd(BiPy)(0)] formed. The alkyne pna proved to be less effective in the displacement of dmfu than dmbd. The reaction under stoichiometric equimolar conditions of the latter with [Pd(eta(2)-dmfu)(BiPy)] allows the direct determination of the bimolecular self-reaction rate constant k(c) and consequently the assessment of all the rate constants involved in the overall mechanistic network.

  DOI：

  10.1021/om8002398

文献信息

• Stoichiometric and Catalytic Conversion of Alkynes to Conjugated (<i>Z</i>,<i>Z</i>)-Dienes and Cyclopentadienes via Palladacyclopentadienes and 1,3-Dienylpalladium(II) Halide and Triorganopalladium(IV) Halide Compounds Containing Chelating Nitrogen Ligands
  作者：Ruud van Belzen、René A. Klein、Huub Kooijman、Nora Veldman、Anthony L. Spek、Cornelis J. Elsevier

  DOI：10.1021/om970977l

  日期：1998.4.1

  transmetalation with tetramethyltin, a catalytic cycle for the three-component synthesis of (Z,Z)-dienes of the type R−C(E)C(E)C(E)C(E)CH3 (8, R = alkyl, aryl; E = CO2CH3) has been conceived, e.g., from dimethyl 2-butynedioate, an organic halide, and tetramethyltin employing 1% of 1b as the catalyst in DMF. This constitutes the first catalytic synthesis of conjugated dienes from alkynes. Pd(phosphine) compounds

  含有螯合双齿氮配体Pd （C（E）C（E）-C（E）C（E）}（NN）1a - f（E = CO 2 Me，NN =已从Pd（dba）2制备了Ph-bip，Ar-bian，bpy，dcm-bpy，bpym）和2a，b（E = CF 3，NN = Ph-bip，（p -tol）-bian），适当的双齿N-配体和缺电子的炔基2-丁炔二酸二甲酯或六氟丁炔，获得化合物1a（NN = Ph-bip）和1d（NN = 2,2'-bpy）的X射线晶体结构。溶液中，化合物1d的单体和二聚体之间存在平衡和1e（NN =联嘧啶）; 在固态下，1d是单体。1d的二聚体形式与零价钯化合物[（μ-3,3'-二甲氧基-2,2'-联吡啶）Pd（tcne）] 2具有相同的类型，其中两个联吡啶衍生物桥接在两个钯之间由该化合物（7）的X射线晶体结构确定的中心。Palladacycles 1经历甲基碘，苄基溴或碘苯的氧化加成。随后的还原消除引起4官能的1
• The formation of a metallacycloheptadienyl intermediate in the reaction of palladacyclopentadienyl derivatives with tetracyanoethylene
  作者：Luciano Canovese、Fabiano Visentin、Claudio Santo

  DOI：10.1016/j.jorganchem.2007.06.037

  日期：2007.9

  yield under mild conditions the type 2 cycles C6(CN)4R1R2R3R4 and the corresponding palladium(0) olefin derivative [Pd(η2]-TCNE)(LL′)]. The olefin insertion reactions are usually fast, but in the case of the reaction of complex 1Da with TCNE accumulation of an intermediate is observed. The low temperature NOESY spectrum allows the determination of the intermediate structure which can be described as

  类型1 [Pd（LL'）（C 4 R 1 R 2 R 3 R 4）]的钯（II）衍生物（LL'= HNSPh：2-（苯硫甲基）-吡啶（A），BiPy：2， 2′-联吡啶基（B），DPPE：双-二苯基膦基乙烷（C），NEOC：新铜pro（2,2′-二甲基-邻菲咯啉）（D），R 1  = R 4  = COOMe，R 2，R 3  = C 10 H 6（a），R 1  = R 3  = C 6 H 5，R2  = R 4  = COOMe（b），R 1  = R 2  = R 3  = R 4  = COOMe（c））与弱电子烯烃四氰基乙烯（TCNE）反应，在温和条件下产生2型循环C 6（CN ）4 - [R 1 - [R 2 - [R 3 - [R 4和相应的钯（0）烯烃衍生物[钯（η 2 ] -TCNE）（L-L'）。烯烃的插入反应通常很快，但是在1Da络合物的情况下观察到具有TCNE的中
• Formation and coordination modes of the C4E4 moiety (E = COOMe) bound to two palladium(ii) moieties
  作者：Tetsuro Murahashi、Taketoshi Okuno、Kentaro Usui、Kohei Takase、Toshiaki Otani、Sensuke Ogoshi、Hideo Kurosawa

  DOI：10.1039/c0dt01169j

  日期：——

  The transmetallation of the palladacyclopentadiene complex PdC(COOMe)C(COOMe)C(COOMe)C(COOMe)}(bipy) with the dicationic PdII complex [Pd(bipy)(CH3CN)2][BF4]2 afforded a terminally σ-palladated diene complex [Pd2μ-η1:η1-C(COOMe)C(COOMe)C(COOMe)C(COOMe)}(bipy)2(CH3CN)2][BF4]2. It was revealed by X-ray crystallographic analysis that replacement of the acetonitrile ligands in a terminally σ-palladated diene complex with PPh3 ligands resulted in the conformation change of the σ-palladated diene moiety from skewed s-cis to planar s-trans. Treatment of a bis-triphenylphosphine dipalladium complex [Pd2(PPh3)2(CH3CN)4][PF6]2 with dimethoxyacetylene dicarboxylate (DMAD) (1 equiv.) in acetonitrile resulted in the insertion of DMAD to the Pd–Pd bond to afford [Pd2μ-η1:η1-C(COOMe)C(COOMe)}(PPh3)2(CH3CN)4][PF6]2. Addition of the second DMAD gave the ylide-type complex [Pd2μ-η2:η3-C(COOMe)C(COOMe)C(COOMe)C(COOMe)(PPh3)}(PPh3)2(CH3CN)3][PF6]2 of which the structure was determined by X-ray crystallographic analysis.

  将 PdC(COOMe)C(COOMe)C(COOMe)C(COOMe)}(bipy)与二阳离子 PdII 复合物[Pd(bipy)(CH3CN)2][BF4]2 进行反金属化，可得到末端为 σ-palladated 的二烯复合物[Pd2μ-η1：η1-C(COOMe)C(COOMe)C(COOMe)C(COOMe)}(bipy)2(CH3CN)2][BF4]2。X 射线晶体学分析表明，用 PPh3 配体取代末端 σ-palladated 二烯配合物中的乙腈配体，可使 σ-palladated 二烯分子的构象从偏斜的 s-cis 转变为平面的 s-trans。将双三苯基膦二钯配合物 [Pd2(PPh3)2(CH3CN)4][PF6]2与二甲氧基乙炔二羧酸盐（DMAD）（1 equiv.在乙腈中加入二甲氧基乙炔二羧酸盐 (DMAD)（1 等份），DMAD 插入 Pd-Pd 键，得到 [Pd2μ-η1:η1-C(COOMe)C(COOMe)}(PPh3)2(CH3CN)4][PF6]2。加入第二个 DMAD 后，得到了[Pd2μ-η2:η3-C(COOMe)C(COOMe)C(COOMe)C(COOMe)(PPh3)}(PPh3)2(CH3CN)3][PF6]2 的矢量型复合物，其结构已通过 X 射线晶体分析法确定。