trans-[PdEt2(PMe2Ph)2] | 75108-70-2

• 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: trans-[PdEt2(PMe2Ph)2]
• 英文别名: trans-PdEt2(PMe2Ph)2；trans-[PdEt₂(PMe₂Ph)₂]；trans-[(PMe2Ph)2PdEt2]
• CAS: 75108-70-2
• 化学式: C₂₀H₃₂P₂Pd
• 分子量: 440.842
• InChiKey: AOPHDXIOTYAKBD-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.05
• 重原子数：
  23.0
• 可旋转键数：
  6.0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.4
• 拓扑面积：
  0.0
• 氢给体数：
  0.0
• 氢受体数：
  0.0

反应信息

• 作为反应物：
  描述：

  trans-[PdEt2(PMe2Ph)2] 在 盐酸 作用下， 以 乙醚 为溶剂， 生成 trans-PdEt(Cl)(PMe2Ph)2
  参考文献：
  名称：

  Ozawa, Fumiyuki; Sugimoto, Takeshi; Yuasa, Yasuhiro, Organometallics, 1984, vol. 3, # 5, p. 683 - 692

  摘要：

  DOI：
• 作为产物：
  描述：

  cis-Et2bis(dimethylPhphosphine)palladium(II) 以 甲苯 为溶剂， 以2%的产率得到trans-[PdEt2(PMe2Ph)2]
  参考文献：
  名称：

  Ozawa, Fumlyuki, Organometallics, 1992, vol. 1, # 11, p. 1481 - 1485

  摘要：

  DOI：

文献信息

• Reactivity of the bis(silyl) palladium(II) complex toward organic isothiocyanates
  作者：Yong-Joo Kim、Hyung-Tak Jeon、Kyung-Eun Lee、Soon W. Lee

  DOI：10.1016/j.jorganchem.2010.06.013

  日期：2010.9

  The bis(silyl) palladium(II) complex [Pd(SiHPh2)2(dmpe)] (dmpe = 1,2-bis(dimethylphosphino)ethane) reacted with organic isothiocyanates R–NCS (R = Ph, iPr, allyl) to give a dithiocarbonimidato [Pd(S2CN–Ph)(dmpe)] (1), a diphenylsilanedithiolato [Pd(S2SiPh2)(dmpe)] (2), or a π-allyl [(η3-allyl)Pd](NCS) (3) palladium complex, depending on the isothiocyanate type and reaction conditions. In addition,

  双（甲硅烷基）钯（II）配合物[Pd（SiHPh 2）2（DMPe）]（DMPe = 1,2-双（二甲基膦基）乙烷）与有机异硫氰酸酯R-NCS（R = Ph，i Pr，烯丙基）反应），得到dithiocarbonimidato [钯（S 2 ç N - PH）（DMPE）]（1），一个diphenylsilanedithiolato [钯（S 2 SIPH 2）（DMPE）]（2）或π烯丙基[（η 3 -烯丙基）Pd]（NCS）（3）钯络合物，具体取决于异硫氰酸酯的类型和反应条件。此外，还从反式-[PdEt 2 L 2]（L = PME 3，PME 2 PH）（4 - 6）或[钯（苯乙烯）L- 2 ]和有机异硫氰酸酯。
• Mechanism of thermal decomposition of trans-diethylbis(tertiary phosphine)palladium(II). Steric effects of tertiary phosphine ligands on the stability of diethylpalladium complexes
  作者：Fumiyuki Ozawa、Takashi Ito、Akio Yamamoto

  DOI：10.1021/ja00541a013

  日期：1980.10

  phosphine. Activation enthalpies for thermolysis of the ethylpalladium complexes having various steric bulkiness were virtually constant in the range of 26.0 +- 1.0 kcal/mol whereas activation entropies showed considerable variation with increasing bulkiness of the phosphine. Thermolysis of trans-(Pd(CH/sub 2/CD/sub 3/)/sub 2/(PMePh/sub 2/)/sub 2/) cleanly liberated CH/sub 2/==CD/sub 2/ and CH/sub 2/DCD/sub

  trans-(PdR'/sub 2/(PR/sub 3/)/sub 2/) 具有一系列烷基和各种空间体积的叔膦配体 (R' = Et, PR/sub 3/ = PMe/sub 2/Ph、PEt/sub 3/、PEt/sub 2/Ph、PMePh/sub 2/、PEtPh/sub 2/；R' = Pr、Bu、PR/sub 3/ = PMe/sub 2/Ph)通过..β..-消除过程在溶液中热解，以 1:1 的比例释放烷烃和烯烃。trans-(PdEt/sub 2/(PR/sub 3/)/sub 2/) 热解的动力学研究表明，它们分解遵守关于钯配合物浓度的一级速率定律。热解主要从四配位络合物进行，而没有叔膦配体的解离。涉及膦解离的次要平行热解途径被膦的加入完全阻断。具有各种空间体积的乙基钯配合物的热解的活化焓实际上恒定在26.0±1.0kcal/mol的范围内，而活化熵随着膦体积的增加而显示出
• Dinuclear palladium–azido complexes containing thiophene derivatives: reactivity toward organic isocyanides and isothiocyanates
  作者：Xiaohong Chang、Mi-Young Kim、Yong-Joo Kim、Hyun Sue Huh、Soon W. Lee

  DOI：10.1039/b616901e

  日期：——

  Cyclopalladated tetranuclear Pd(II) complexes, [Pd2(µ-Cl)2(Y)]2 (Y = L1 or L2; H2L1 = di(2-pyridyl)-2,2′-bithiophene; H2L2 = 5,5″-di(2-pyridyl)-2,2′:5′,2″-terthiophene), containing two pyridyl-α, α′-disubstituted derivatives of thiophene were prepared. Treating these products with PR3 and subsequently with NaN3 produced the dinuclear Pd–azido complexes [(PR3)2(N3)Pd–Y–Pd(N3)(PR3)2] (Y = L1 or L2) or a cyclometallated complex [(PR3)(N3)Pd–Y′–Pd(N3)(PR3)] (Y′ = C,N-L2). Reactions of these Pd–azido complexes with CN–Ar (Ar = 2,6-Me2C6H3, 2,6-i-Pr2C6H3) or R–NCS (R = i-Pr, Et, allyl) led to the complexes containing end-on carbodiimido groups [(PMe3)2(NCN–Ar)Pd–Y–Pd(NCN–Ar)(PMe3)2] or S-coordinated tetrazole-thiolato groups (PMe3)2[CN4(R)]S–Pd–Y–Pd–S[CN4)(R)](PMe3)2}. Interestingly, when treated with elemental sulfur, the carbodiimido complexes transformed into the cyclometallated derivatives, [(PMe3)(NCN–Ar)Pd–Y′–Pd(NCN–Ar)(PMe3)] (Y′ = C,N-L1, C,N-L2). We also report the preparation of linear, thienylene-bridged dinuclear Pd complexes [L2(N3)Pd–X(or X′)–Pd(N3)L2] (L = PMe3 or PMe2Ph; H2X = 2,2′-bithiophene or H2X′ = 2,2′:5′,2″-terthiophene) and their reactivity toward organic isocyanide and isothiocyanates.

  含两个吡啶基-α,α'-二取代噻吩衍生物的环钯化四核铂(II)配合物,[Pd2(μ-Cl)2(Y)]2(Y=L1或L2;H2L1=二(2-吡啶基)-2,2'-联噻吩;H2L2=5,5''-二(2-吡啶基)-2,2':5',2''-三联噻吩)已被合成。将这些产物与PR3反应,随后与NaN3反应,得到双核Pd-叠氮配合物[(PR3)2(N3)Pd-Y-Pd(N3)(PR3)2](Y=L1或L2)或环金属化配合物[(PR3)(N3)Pd-Y'-Pd(N3)(PR3)](Y'=C,N-L2)。这些Pd-叠氮配合物与CN-Ar(Ar=2,6-Me2C6H3,2,6-i-Pr2C6H3)或R-NCS(R=i-Pr,Et,烯丙基)反应,生成含端基卡宾二亚胺[(PMe3)2(NCN-Ar)Pd-Y-Pd(NCN-Ar)(PMe3)2]或硫配位的四唑硫醇盐[(PMe3)2[CN4(R)]S-Pd-Y-Pd-S[CN4)(R)](PMe3)2]的配合物。有趣的是,当与元素硫反应时,卡宾二亚胺配合物转化为环金属化衍生物[(PMe3)(NCN-Ar)Pd-Y'-Pd(NCN-Ar)(PMe3)](Y'=C,N-L1,C,N-L2)。我们还报道了制备线性噻吩桥连双核Pd配合物[L2(N3)Pd-X(或X')-Pd(N3)L2](L=PMe3或PMe2Ph;H2X=2,2'-联噻吩或H2X'=2,2':5',2''-三联噻吩)及其与有机异氰和异硫氰的反应性。
• Cyclic tetramers of a five-membered palladacycle based on a head-to-tail-linked isocyanate dimer and their reactivity in cyclotrimerization of isocyanates
  作者：Seon Gye Lee、Keun-Young Choi、Yong-Joo Kim、SuJin Park、Soon W. Lee

  DOI：10.1039/c5dt00534e

  日期：——

  Reactions of [Pd(styrene)(PR3)2], generated from trans-[PdEt2(PR3)2] and styrene, with 2 equiv. of benzyl isocyanate in THF at room-temperature afforded unusual cyclic Pd-tetramers of five-membered rings consisting of organic isocyanate dimers and palladium, [Pd(PR3)–C(O)N(R)C(O)N(R)–}]4 (PR3 = PMe3, 1; PR3 = PMe2Ph, 2). Additionally, a cyclic trimer, (RNCO)3, 3 (R = benzyl) was produced as a catalytic

  的反应[钯（苯乙烯）（PR 3）2 ]，从生成的反式- [PDET 2（PR 3）2 ]和苯乙烯，与2当量 室温下将异氰酸苄酯在THF中制得的五元环的非常规环状Pd-四聚体由有机异氰酸酯二聚体和钯组成，[Pd（PR 3）– C（O）N（R）C（O）N（ R） - }] 4（PR 3 = PME 3，1 ; PR 3 = PME 2 PH，2）。另外，环状三聚体，（RNCO）3，3（R ＝苄基）作为催化产物产生。用4当量处理环状四聚体（1）。（1,2-双（二乙基膦基）乙烷）（DEPE）或（1,2-双（二甲基膦基）乙烷）（DMPE）等螯合膦容易引起金属环顺式[Pd N （R）C（O）N（R）C（O）}（P〜P）]（P〜P = DEPE，4 ; P〜P = DMPE，5）以定量产率计算。相反，Pd（0）-PR 3与2当量的反应。N- CO （Ar = Ph，p - tolyl ，p -ClC
• Macrocyclic complexes containing a platinacycle or palladacycle composed of an isocyanate dimer unit: Reactivity towards isocyanides and cyclotrimerization of isocyanates
  作者：Jun-Hwan Choi、Kang-Yeoun Jung、Yong-Joo Kim、Hye Jin Im、Soon W. Lee

  DOI：10.1016/j.poly.2016.05.061

  日期：2016.10

  cyclic products as an assembly of four platinacycles or palladacycles, [M(PR3)–N(R)C(O)N(R)C(O)–}]4, were readily obtained. These cyclic tetramers were cleaved using tert-butyl isocyanide (CN–tbutyl, 4 equiv.), affording the corresponding monomeric complexes, [M(PR3)(CN–tbutyl)–N(R)C(O)N(R)C(O)–}] (M = Pt, Pd). An unusual cyclotrimerization of organic isocyanates catalyzed by zerovalent Pt complexes

  摘要[Pt（苯乙烯）（PMe3）2]与2当量的反应。的五元铂盐环烷基或芳基异氰酸酯，顺式-[Pt –N（R）C（O）N（R）C（O）–}（PMe3）2]（R = CH2C6H5，p-ClC6H4，p -OMeC6H4）。这些络合物是含有异氰酸酯二聚体单元的铂环化合物的第一个实例。当五元双（膦）platinacycles或palladacycles用2当量处理时。容易获得由四个platinacycles或palladacycles，[M（PR3）– N（R）C（O）N（R）C（O）–}] 4组成的元素硫，16元环状产物。这些环状四聚体使用叔丁基异氰化物（CN-叔丁基，当量为4当量）裂解，得到相应的单体络合物，[M（PR3）（CN-叔丁基）– N（R）C（O）N（R） C（O）–}]（M = Pt，Pd）。观察到由零价Pt络合物或五元铂环化合物催化的有机异氰酸酯的异常环三聚。此外，还研究