tetrakis(triphenylarsine)palladium(0) | 23732-79-8

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: tetrakis(triphenylarsine)palladium(0)
• 英文别名: tetrakis(triphenylarsine)palladium；Pd(AsPh₃)₄；Pd(AsPh₃)₄；Pd(triphenylarsene3)4；Pd(AsPh3)4；Pd(Ph3As)4；Palladium;triphenylarsane；palladium;triphenylarsane
• CAS: 23732-79-8
• 化学式: C₇₂H₆₀As₄Pd
• 分子量: 1331.37
• InChiKey: ZKOQRYHTOIASRB-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  8.81
• 重原子数：
  77
• 可旋转键数：
  12
• 环数：
  12.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  0

反应信息

• 作为反应物：
  描述：

  1,3-丙酮二羧酸二甲酯 、 tetrakis(triphenylarsine)palladium(0) 在 air 作用下， 以 苯 为溶剂， 以93%的产率得到2,4-bis(methoxycarbonyl)-1,1-bis(triphenylarsine)palladacyclobutan-3-one-water(1/1)
  参考文献：
  名称：

  金属环丁酮的化学。第2部分。钯的一些高度起皱的金属单环丁烷3-1（氧代二亚甲基甲烷）配合物的合成和环转化。2,4-双（甲氧基羰基）-1,1-双（三苯基膦）钯环丁烷-3-one，2,4-双（甲氧基羰基）-1,1-双（三苯基s）钯环丁烷-3-酮的晶体结构1,1-（2'，2''-联吡啶基）-2,4-双（甲氧基羰基）Palladacyclobutan-3-one

  摘要：

  零价钯络合物[Pd 2（dba）3 ]·CHCl 3（dba =二亚苄基丙酮，PhCH CH–C（O）–CH CHPh）在供体配体L和双氧存在下与酯的反应的3-氧戊二烯酸（RCH 2 COCH 2 R）在乙醚中的制备，高收率得到了Pallada-cyclobutan-3-one化合物[P [graphic省略] HR）L 2 ] [R = CO 2 Me，L = PPH 3，PMePh 2，PME 2 PH，PET 3，或ASPH 3，L 2 = 2,2'-联吡啶（联吡啶）; R = CO 2 Et，L = PPh 3或AsPh 3，L 2 = bipy；R ＝ CO 2 Pr n，L 2＝ bipy]。在用RCH 2 COCH 2处理[PdL 4 ]的苯溶液时，也形成了化合物[P [图示] HR）L 2 ]（R = CO 2 Me或CO 2 Et，L = PPh 3或AsPh 3）。R在空气中存在。用苯中的[Pd（O

  DOI：

  10.1039/dt9850000259
• 作为产物：
  描述：

  tris(dibenzylideneacetone)dipalladium(0) chloroform complex 、 三苯胂 以 乙醚 为溶剂， 以97%的产率得到tetrakis(triphenylarsine)palladium(0)
  参考文献：
  名称：

  金属环丁酮的化学。第2部分。钯的一些高度起皱的金属单环丁烷3-1（氧代二亚甲基甲烷）配合物的合成和环转化。2,4-双（甲氧基羰基）-1,1-双（三苯基膦）钯环丁烷-3-one，2,4-双（甲氧基羰基）-1,1-双（三苯基s）钯环丁烷-3-酮的晶体结构1,1-（2'，2''-联吡啶基）-2,4-双（甲氧基羰基）Palladacyclobutan-3-one

  摘要：

  零价钯络合物[Pd 2（dba）3 ]·CHCl 3（dba =二亚苄基丙酮，PhCH CH–C（O）–CH CHPh）在供体配体L和双氧存在下与酯的反应的3-氧戊二烯酸（RCH 2 COCH 2 R）在乙醚中的制备，高收率得到了Pallada-cyclobutan-3-one化合物[P [graphic省略] HR）L 2 ] [R = CO 2 Me，L = PPH 3，PMePh 2，PME 2 PH，PET 3，或ASPH 3，L 2 = 2,2'-联吡啶（联吡啶）; R = CO 2 Et，L = PPh 3或AsPh 3，L 2 = bipy；R ＝ CO 2 Pr n，L 2＝ bipy]。在用RCH 2 COCH 2处理[PdL 4 ]的苯溶液时，也形成了化合物[P [图示] HR）L 2 ]（R = CO 2 Me或CO 2 Et，L = PPh 3或AsPh 3）。R在空气中存在。用苯中的[Pd（O

  DOI：

  10.1039/dt9850000259
• 作为试剂：
  描述：

  2,2'-联二噻吩 、 2,5-dibromo-3,4-dihexylthiophene-1,1-dioxide 在 正丁基锂 、 三丁基氯化锡 、 tetrakis(triphenylarsine)palladium(0) 作用下， 以 甲苯 为溶剂， 反应 8.0h， 以0.20 g的产率得到2-bromo-3,4-dihexyl-5-[5-(2,2'-bithienyl)]thiophene-1,1-dioxide
  参考文献：
  名称：

  Oligothiophene Isothiocyanates as a New Class of Fluorescent Markers for Biopolymers

  摘要：

  The regioselective synthesis of fluorescent oligothiophene isothiocyanates is described. The isothiocyanates were reacted with bovine serum albumin (BSA) following standard procedures and the optical properties of the oligothiophene-BSA conjugates were analyzed as a function of oligomer concentration, time, and irradiation power. The oligothiophene-BSA conjugates were chemically very stable and their photoluminescence characteristics persisted unaltered for several months. Photoluminescence data relative to the conjugate of an oligothiophene-S,S-dioxide isothiocyanate with monoclonal anti-CD8 antibody are reported. No fluorescence quenching was observed following the binding of the isothiocyanate to the antibody and the conjugate displayed high chemical stability and photostability.

  DOI：

  10.1021/ja011209v

文献信息

• Preparation, Structure, and Reactivity of Dipalladium(I) Complexes Containing the Carbanion 2-C₆F₄PPh₂: Coexistence of Distinct, Noninterconverting Head-to-Head [Dipalladium(0/II)] and Head-to-Tail [Dipalladium(I)] Species
  作者：Suresh K. Bhargava、Steven H. Privér、Anthony C. Willis、Martin A. Bennett

  DOI：10.1021/om300525p

  日期：2012.8.13

  weaker metal–metal interaction in the dimetal(II) complexes. Unexpectedly, reaction of 5 with iodobenzene gives a mononuclear palladium(II) complex, cis-[Pd(κ2C,P-2-C6F4PPh2)(κC-2-C6F4PPh2)(PPh3)] (15). This is suggested to be formed by a sequence of (a) oxidative addition of iodobenzene to 5 to give a σ-phenyl complex analogous to the σ-methyl complex 14, (b) a change in the binding mode of one of

  的歧化反式- [钯（κ 2 -2-C 6 ˚F 4 PPH 2）2 ]与[PDL 4 ]（L = PPH 3，ASPH 3）给出的金属-金属键合二钯（I）配合物[钯2我（μ-2- C6 F 4 PPh 2）2（L）2 ] [L ＝ PPh 3（5），ASPh 3（6）]，其中，桥连配体采用头尾相接的方式。相应的二铂（I）络合物[PT 2 I（μ-2-C6 ˚F 4 PPH 2）2（PPH 3）2 ]（9）类似地从[PT获得（κ 2 -2-C 6 ˚F 4 PPH 2）2 ]和[铂（PPH 3）3 ]。二钯（I）配合物[2.5740（3）Å（5），2.5511（3）Å（6）]中金属原子之间的间隔略小于二铂（I）配合物9 [2.61179（15）]一种]。6的轴向三苯ar基配体被叔取代丁基异氰酸酯，得到二钯（I）络合物[Pd 2 I（μ-2- C6 F 4 PPh 2）2（CN t Bu）2 ]（7）。然而，治疗的反式-
• Mechanism of the Stille Reaction. 2. Couplings of Aryl Triflates with Vinyltributyltin. Observation of Intermediates. A More Comprehensive Scheme
  作者：Arturo L. Casado、Pablo Espinet、Ana M. Gallego

  DOI：10.1021/ja001511o

  日期：2000.12.1

  The mechanism of the [PdL4]-catalyzed couplings between R-OTf (R = pentahalophenyl; L = PPh3, AsPh3) and Sn(CH=CH2)Bu-3 has been studied. The addition of LiCl favors the coupling for L = AsPh3 in THF but retards it for L = PPh3. Separate experiments show that for L = AsPhs, LiCl accelerates the otherwise very slow and rate-determining oxidative addition of the aryl triflate to [PdL4], leading to trans[PdRClL2]. Therefore, the overall process is accelerated. For L = PPh3, the rate-determining step is the transmetalation. Complex trans-[PdRXL2],with X = Cl, is formed in the presence of LiCl, whereas an equilibrium mixture mainly involving species with X = TfO, L, or S (S = solvent) is established in the absence of LiCl. Since the transmetalation is slower for X = Cl than for the other complexes, the overall process is retarded by addition of LiCl. The transmetalation in complexes trans-[PdRXL2], with X = Cl, follows the S(E)2(cyclic) mechanism proposed in Part 1 (Casado, A. L.; Espinet, P. J. Am. Chem. Sec. 1998, 120, 8978-8985), giving the coupling product R-CH=CH2 directly. For X = TfO or, L rather stable intermediates trans[PdR(CH=CH2)L-2] are detected, Supporting an SE2(open) mechanism. The I;ey:intermediates undergoing transmetalation in the conditions arid solvents most commonly used in the literature have been identified.;The operation of S(E)2(cyclic) and S(E)2(open) pathways emphasizes common aspects of the Stille reaction with the Hiyama reaction where, using (RSiF3)-Si-2 that is chiral at the alpha -carbon of R retention or inversion gt the transmetalated chiral carbon can be-induced. This helps us to understand the contradictory stereochemical outcomes in the literature for Stille couplings using (RSnR3)-Sn-2 derivatives that are chiral Bt the a-carbon of R-2 and suggests that stereocontrol of the Stille reaction might be achieved.
• Mednikov, E. G.; Eremenko, N. K., Koordinatsionnaya Khimiya, 1986, vol. 12, p. 461 - 465
  作者：Mednikov, E. G.、Eremenko, N. K.

  DOI：——

  日期：——
• Synthesis and optical properties of a poly(2′,5′-dioctyloxy-4,4′,4″- terphenylenevinylene) with high content of (Z) vinylene units
  作者：Francesco Babudri、Antonio Cardone、Tiziana Cassano、Gianluca M. Farinola、Francesco Naso、Raffaele Tommasi

  DOI：10.1016/j.jorganchem.2008.05.014

  日期：2008.7

  Poly(2',5'-dioctyloxy-4,4',4 ''-terphenylenevinylene) with (E) configuration of the vinylene double bonds was prepared by Suzuki -Miyaura polymerization of (E)-4,4'-dibromostilbene and 2,5-dioctyloxy-1,4-benzenediboronic acid. Attempts to extend this simple procedure to the synthesis of the polymer with (Z) configuration, starting from (Z)-4,4'-dibromostilbene, were unsuccessful. However, the use of (Z)4,4'- diiodostilbene and a careful choice of Pd catalyst and experimental conditions, lead to a material with a > 95/< 5 (Z)/(E) ratio of vinylene units. The investigation of optical properties of both the (E) and (Z) polymers evidenced that (Z) linkages act as defects which reduce the effective conjugation length in the polymer backbone. (C) 2008 Elsevier B.V. All rights reserved.