trans-Pt(CH2C.tplbond.CPh)(Cl)(PPh3)2 | 199061-55-7

• 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-Pt(CH2C.tplbond.CPh)(Cl)(PPh3)2
• 英文别名: trans-[Pt(η(1)-CH2CCPh)(Cl)(PPh3)2]；trans-[Pt(PhC.tplbond.CCH2)(Cl)(PPh3)2]；Chloroplatinum(1+);propa-1,2-dienylbenzene;triphenylphosphane
• CAS: 199061-55-7；174276-83-6；174391-11-8；174276-78-9
• 化学式: C₄₅H₃₇ClP₂Pt
• 分子量: 870.269
• InChiKey: VSBFJMHAMVAEME-UHFFFAOYSA-M

计算性质

• 辛醇/水分配系数(LogP)：
  9.76
• 重原子数：
  49
• 可旋转键数：
  7
• 环数：
  7.0
• 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：
  1

反应信息

• 作为反应物：
  描述：

  trans-Pt(CH2C.tplbond.CPh)(Cl)(PPh3)2 、 lithium phenylacetylide 以 四氢呋喃 为溶剂， 以50%的产率得到cis-Pt(CH2C.tplbond.CPh)(C.tplbond.CPh)(PPh3)2
  参考文献：
  名称：

  Mechanistic studies on mutual isomerization of propargyl- and allenylplatinum(II) complexes

  摘要：

  When heated in benzene, phenyl-substituted propargylplatinum(II) complexes, trans-Pt(CH2C drop CPh) (X) (PPh3)(2) (2) (X=Cl, Br, I), isomerized gradually to the more stable allenyl isomers, trans-Pt(CPh=C=CH2) (X) (PPh3)(2) (3), to give rise to an equilibrium mixture of 2/3 (5/95), from which 3 (X = Cl) was isolated as an isomerically pure sample. The allenyl complex 3 also gave rise to the same equilibrium mixture of 2/3 when heated under the same conditions. The rate of propargyl-to allenylplatinum(II) isomerization was examined as the function of the ligand X in 2. The isomerization rate was first-order in the concentration of the propargyl complex, not affected by adding PPh3, and increased in the order X = Cl < Br < I. The organo(propargyl)platinum(II) complex, cis-Pt(CH2C drop CPh) (C drop CPh) (PPh3)(2), isomerized even faster to the corresponding allenyl isomer than 2. These kinetic aspects led us to suggest that the spontaneous propargyl-to allenylplatinum isomerization proceeds via intramolecular rearrangement of an 18-electron eta(3)-propargyl/allenyl intermediate, Pt(eta(3)-CH2C drop CPh) (X) (PPh3)(2). The isomerization from 2 to 3 was accelerated considerably by addition of Pt(PPh3)(2)L-n (L=PPh3, n=2; L=C2H4, n=1), but not at all by addition of PtCl2(PPh3)(2). (C) 1997 Elsevier Science S.A.

  DOI：

  10.1016/s0020-1693(97)05706-x
• 作为产物：
  描述：

  四丁基氯化铵 、 [(PPh3)2Pt(η(3)-CH2CCPh)](CF3SO3) 以 二氯甲烷-D2 为溶剂， 生成 trans-Pt(CH2C.tplbond.CPh)(Cl)(PPh3)2
  参考文献：
  名称：

  Kinetic Evidence for π-Complex Formation Prior to Oxidative Addition of Propargyl Halides to Triphenylphosphine−Platinum(0) Complexes

  摘要：

  The mechanism of oxidative addition of phenylpropargyl halides to Pt(PPh3)(4) to give Pt(eta (1)-CH2C=CPh)(X)(PPh3)(2) has been investigated on the basis of the kinetics of the reaction and stereomeric analysis of the products. The kinetic results of the reaction showed the contributions of two pathways involving Pt(PPh3)(3) and Pt(PPh3)(3) complexes as active species. The second-order rate constants for both pathways were on the order of 10(3) larger than the corresponding rate constants of the oxidative addition reaction of CH3I, Moreover, both active species and the substrate halide gave, as the kinetic product, the isomer having two PPh3 groups located cis, which is also in sharp contrast to the case of the reaction of CH3I. It is proposed that the rate-determining step in the reaction involving Pt(PPh3)(2) is the coordination of the C=C bond to Pt(PPh3)(2) to form Pt(eta (2)-PhC=CCH2X)(PPh3)(2), which subsequently undergoes rapid collapse to the eta (3)-propargyl complex [Pt(eta (3)-CH2CCPh)(PPh3)(2)]X and eventually to cis-Pt(eta (1)-CH2C=CPh)(X)(PPh3)(2). The reaction of Pt(PPh3)(3) may also involve a rate-determining C=C bond coordination step.

  DOI：

  10.1021/om000376l

文献信息

• Structure-Reactivity Relationship in Allyl and 2-Propynyl Complexes of Group 10 Metals Relevant to Homogeneous Catalysis
  作者：Hideo Kurosawa、Sensuke Ogoshi

  DOI：10.1246/bcsj.71.973

  日期：1998.5

  propargyl (2-propynyl) complexes are described. Emphasis was placed on the bonding-reactivity relationship of these complexes which are relevant as key intermediate models in transition metal catalyzed transformations of allylic and propargylic substrates as well as related transformations involving unsaturated hydrocarbons. The specific complexes surveyed include group 10 metal complexes of allyl and propargyl

  描述了对 10 族金属烯丙基和炔丙基（2-丙炔基）配合物所经历的一些基本反应的理解的最新进展。重点放在这些配合物的键合反应性关系上，这些配合物与过渡金属催化烯丙基和炔丙基底物的转化以及涉及不饱和烃的相关转化中的关键中间模型有关。调查的特定配合物包括以 η1 和 η3 方式与金属结合的烯丙基和炔丙基配体的第 10 族金属配合物。要讨论的具体反应包括氧化加成、烯丙基或炔丙基配体的亲核和亲电攻击，以及烯丙基配体的还原消除。
• Intermolecular propargyl/allenyl group transfer from Pd(II) to Pt(0) and Pt(II) to Pd(0). Key reaction in metal-catalyzed isomerization between propargyl and allenyl metal complexes
  作者：Sensuke Ogoshi*、Takuma Nishida、Yoshiaki Fukunishi、Ken Tsutsumi、Hideo Kurosawa*

  DOI：10.1016/s0022-328x(00)00787-7

  日期：2001.2

  Isomerization of phenyl-substituted propargylplatinum(II) complex, trans-Pt(CH2CCPh)(Cl)(PPh3)2 (1) to allenyl complex, trans-Pt(CPhCCH2)(Cl)(PPh3)2 (2) was found to be catalyzed by zerovalent complex Pd(PPh3)4. The reaction was proposed to proceed through the transfer of the propargyl/allenyl ligand both from Pt(II) to Pd(0) and Pd(II) to Pt(0). The former transfer, which seemingly has a thermodynamic

  苯基取代propargylplatinum的异构化（II）配合物，反式铂（CH 2 CCPh）（CL）（PPH 3）2（1）到丙二烯基配合物，反式-Pt（CPhCCH 2）（Cl）的发现（PPh 3）2（2）被零价络合物Pd（PPh 3）4催化。建议该反应通过将炔丙基/烯丙基配体既从Pt（II）转移到Pd（0），又从Pd（II）转移到Pt（0）而进行。显然已证实发生了前一种转移，该转移似乎具有热力学缺点。Pd（PPh）治疗13）4或Pd的混合物2（DBA）3和PPH 3导致的Pd的形成（I）络合物，钯2（μ-PhCCCH 2）（μ-Cl）的（PPH 3）2，其位于平衡与炔丙基/烯丙基钯（II）和钯（0）配合物的混合物。
• Mutual isomerization of η¹-allenyl and η¹-propargyl complexes of platinum via a five-coordinate η³-allenyl/propargyl intermediate
  作者：Sensuke Ogoshi、Yoshiaki Fukunishi、Ken Tsutsumi、Hideo Kurosawa

  DOI：10.1039/c39950002485

  日期：——

  The reversible spontaneous isomerization between η1-allenyl and η1-propargylplatinum complexes is reported, which is suggested to proceed via pseudorotation of a five-coordinate η3-allenyl/propargyl intermediate.

  报告了δ-1-异戊烯基和δ-1-丙炔基铂络合物之间的可逆自发异构化，并认为这种异构化是通过五配位δ-3-异戊烯基/丙炔基中间体的假otation进行的。
• Kinetic Evidence for π-Complex Formation Prior to Oxidative Addition of Propargyl Halides to Triphenylphosphine−Platinum(0) Complexes
  作者：Takuma Nishida、Sensuke Ogoshi、Ken Tsutsumi、Yoshiaki Fukunishi、Hideo Kurosawa

  DOI：10.1021/om000376l

  日期：2000.10.1

  The mechanism of oxidative addition of phenylpropargyl halides to Pt(PPh3)(4) to give Pt(eta (1)-CH2C=CPh)(X)(PPh3)(2) has been investigated on the basis of the kinetics of the reaction and stereomeric analysis of the products. The kinetic results of the reaction showed the contributions of two pathways involving Pt(PPh3)(3) and Pt(PPh3)(3) complexes as active species. The second-order rate constants for both pathways were on the order of 10(3) larger than the corresponding rate constants of the oxidative addition reaction of CH3I, Moreover, both active species and the substrate halide gave, as the kinetic product, the isomer having two PPh3 groups located cis, which is also in sharp contrast to the case of the reaction of CH3I. It is proposed that the rate-determining step in the reaction involving Pt(PPh3)(2) is the coordination of the C=C bond to Pt(PPh3)(2) to form Pt(eta (2)-PhC=CCH2X)(PPh3)(2), which subsequently undergoes rapid collapse to the eta (3)-propargyl complex [Pt(eta (3)-CH2CCPh)(PPh3)(2)]X and eventually to cis-Pt(eta (1)-CH2C=CPh)(X)(PPh3)(2). The reaction of Pt(PPh3)(3) may also involve a rate-determining C=C bond coordination step.
• Mechanistic studies on mutual isomerization of propargyl- and allenylplatinum(II) complexes
  作者：Sensuke Ogoshi、Yoshiaki Fukunishi、Ken Tsutsumi、Hideo Kurosawa

  DOI：10.1016/s0020-1693(97)05706-x

  日期：1997.11

  When heated in benzene, phenyl-substituted propargylplatinum(II) complexes, trans-Pt(CH2C drop CPh) (X) (PPh3)(2) (2) (X=Cl, Br, I), isomerized gradually to the more stable allenyl isomers, trans-Pt(CPh=C=CH2) (X) (PPh3)(2) (3), to give rise to an equilibrium mixture of 2/3 (5/95), from which 3 (X = Cl) was isolated as an isomerically pure sample. The allenyl complex 3 also gave rise to the same equilibrium mixture of 2/3 when heated under the same conditions. The rate of propargyl-to allenylplatinum(II) isomerization was examined as the function of the ligand X in 2. The isomerization rate was first-order in the concentration of the propargyl complex, not affected by adding PPh3, and increased in the order X = Cl < Br < I. The organo(propargyl)platinum(II) complex, cis-Pt(CH2C drop CPh) (C drop CPh) (PPh3)(2), isomerized even faster to the corresponding allenyl isomer than 2. These kinetic aspects led us to suggest that the spontaneous propargyl-to allenylplatinum isomerization proceeds via intramolecular rearrangement of an 18-electron eta(3)-propargyl/allenyl intermediate, Pt(eta(3)-CH2C drop CPh) (X) (PPh3)(2). The isomerization from 2 to 3 was accelerated considerably by addition of Pt(PPh3)(2)L-n (L=PPh3, n=2; L=C2H4, n=1), but not at all by addition of PtCl2(PPh3)(2). (C) 1997 Elsevier Science S.A.