(dicyclopentadiene)platinum(II) dichloride | 12083-92-0

• 物质功能分类: 化学试剂 - 有机试剂 - 烯烃（环状与无环状）
• 分子结构分类: 有机化合物 - 有机盐 - 有机金属盐
• 英文名称: (dicyclopentadiene)platinum(II) dichloride
• 英文别名: [Pt(dicyclopentadiene)Cl2]；(dicyclopentadiene)platinum(II) chloride；[(η4-dicyclopentadiene)PtCl2]；dichloroplatinum;(1R,2S,6R,7S)-tricyclo[5.2.1.02,6]deca-3,8-diene
• CAS: 12083-92-0
• 化学式: C₁₀H₁₂Cl₂Pt
• 分子量: 398.191
• InChiKey: WGIHWYYQPYXMJF-OYUHCJDISA-L

物化性质

• 熔点：
  220-222 °C

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

安全信息

• 危险品标志：
  Xn
• 危险类别码：
  R36/37/38
• WGK Germany：
  3
• 安全说明：
  S26,S36/37/39
• 危险标志：
  GHS07
• 危险性描述：
  H302
• 危险性防范说明：
  P280,P305+P351+P338

反应信息

• 作为反应物：
  描述：

  (dicyclopentadiene)platinum(II) dichloride 在 KSCN 作用下， 以 丙酮 为溶剂， 以50%的产率得到[(Pt(endo-5σ,2π-exo-6-isothiocyanato-3a,4,7,7a-tetrahydro-endo-methanoindenyl)(SCN))2]
  参考文献：
  名称：

  涉及过渡金属的反应。第十一部分。亲核试剂与二烯铂配合物的反应

  摘要：

  研究了配合物[Pt（二烯）Cl 2 ]（二烯=降冰片二烯或二环戊二烯）与亲核试剂OPr i–，NH 2 Ph，SPh –和SCN –的反应。在每种情况下，二环戊二烯配合物都会受到二烯的攻击，S-亲核试剂也会在铂上产生取代。降冰片二烯配合物和S-亲核试剂仅发生过反应，但OPr i–和NH 2会发现对有机配体的攻击这些产品与中性单齿和双齿配体的反应通常会导致桥裂反应，但在某些情况下，降冰片烯基衍生物会发生重排，变为降冰片烯系统。描述了烯基配合物与其他亲核试剂（OMe –或NHPh –）的反应，以生成双σ键的亚烷基铂配合物。

  DOI：

  10.1039/dt9760002355
• 作为产物：
  描述：

  dichlorobis(diethyl sulfide)platinum 在 endo-dicyclopentadiene 作用下， 以 neat (no solvent) 为溶剂， 以40%的产率得到(dicyclopentadiene)platinum(II) dichloride
  参考文献：
  名称：

  带有二烯烃配体的阳离子钯和铂配合物

  摘要：

  由[M（二烯烃）Cl 2 ] [M ＝ Pd或Pt； [M ＝ Pd]或[Pt]；氯桥联的[M 2（二烯烃）2 Cl 2 ] [BF 4 ] 2。二烯烃＝环辛基-1，5-二烯（cod）或降冰片烯2，5-二烯（nbd）]和[Et 3 O] [BF 4 ]。络合物[Pd（cod）2 Cl 2 ] [BF 4 ] 2迅速形成5,6-η-环-辛-5-烯基络合物[Pd 2（2-Rcot）2 Cl 2 ]（R = MeO，MeCO 2，或HO）与MeOH，MeCO 2 H或H 2 O；PPh 3取代鳕鱼以形成[Pd 2 Cl 2（PPh 3）4 ] [BF 4 ] 2，而植物提取物类似物形成[Pt（cod）Cl（PPh 3）] [BF 4 ]。从sym，反式-[M 2 Cl 4（PR 3）2 ]和具有SFO的二烯烃获得了配合物[M（二烯烃）Cl（PR 3）] X（X = SFO 3，BF 4或ClO 4）2（OMe）–C

  DOI：

  10.1039/dt9760000289
• 作为试剂：
  描述：

  三乙氧基硅烷 、 N-allyl-N-phenylaniline 在 (dicyclopentadiene)platinum(II) dichloride 作用下， 反应 20.0h， 以81%的产率得到N-phenyl-N-(3-(triethoxysilyl)propyl)aniline
  参考文献：
  名称：

  （二环戊二烯）二氯化铂（II）：烯烃与三乙氧基硅烷之间氢化硅烷化反应的有效催化剂

  摘要：

  （二环戊二烯）二氯化铂（II）被发现是一种有效的氢化硅烷化催化剂（均相），适用于多种官能化的烯烃和以化学部分（二苯基氨基，N-咔唑-和N-异二氢吲哚-1,3-终止）的烯烃dione-）。值得注意的是，胺化烯烃与三乙氧基硅烷的氢化硅烷化显示出超过70％的收率和超过3/1的选择性（γ-异构体/β-异构体）。由于空间障碍降低了马尔可夫尼科夫概率，具有大末端部分的烯烃（二苯基氨基，N-咔唑-和N-异吲哚啉-1,3-二酮-）呈现出较高的抗马尔可夫尼科异构体比例。开发了保护的二氨基螯合烯烃的氢化硅烷化策略。

  DOI：

  10.1016/j.tetlet.2017.03.017

文献信息

• Preparations and ligand displacement reactions of diene(polyfluorophenyl)platinum(II) complexes
  作者：G.B. Deacon、K.T. Nelson-Reed

  DOI：10.1016/0022-328x(87)85013-1

  日期：1987.3

  The complexes PtR2(diene) (R = C6F5 or p-HC6F4; diene = cis,cis-cycloocta-1,5-diene (cod), dicyclopentadiene (dcy), norbornadiene (nbd) or hexa-1,5-diene (hex)) have been prepared by the organolithium route. Reaction of PtCl2(cod) with an equimolar amount of TlO2CR (R = C6F5 or p-HC6F4) in pyridine yields Pt(R)Cl(cod), which have been converted into Pt(R)X(cod) (X = Br or I) by halogen exchange reactions

  配合物PtR 2（二烯）（R = C 6 F 5或p -HC 6 F 4 ;二烯=顺式，顺式-环辛-1,5-二烯（鳕鱼），二环戊二烯（dcy），降冰片二烯（nbd）或六-1,5-二烯（hex））已通过有机锂途径制备。PtCl 2（鳕鱼）与等摩尔量的TlO 2 CR（R = C 6 F 5或p -HC 6 F 4）在吡啶中生成Pt（R）Cl（cod），已通过卤素交换反应将其转化为Pt（R）X（cod）（X = Br或I）。其他脱羧导致二烯位移给予顺-Pt（C 6 ˚F 5）氯（PY）2和顺式-和反式-Pt（C 6 ˚F 5）2（PY）2。的配合物，顺式-Pt（C 6 ˚F 5）2大号2（L = PY或PH 3 P）和顺式-Pt（p -HC 6 ˚F 4）2（PPh 3）2）是通过PtR 2（cod）的配体置换反应形成的，但Pt（C 6 F 5）2（cod）不会与N，N，N '，N'-四甲基乙二胺（tmed）反应或Pt（C
• Preparatiions of chloro(diene)polyfluorophenylplatinum(II) complexes and the structure of chloro(dicyclopentadiene)-pentafluorophenylplatinum(II)
  作者：G.B. Deacon、B.M. Gatehouse、K.T. Nelson-Reed

  DOI：10.1016/0022-328x(89)85436-1

  日期：1989.1

  The complexes, PtCl(diene)R (diene = hexa-1,5-diene (hex) or norbornadiene (nbd), R  C6F5, p-HC6F4, or p-MeOC6F4; diene = diene = dicyclopentadiene (dcy), R = C6F5) have been prepared by reaction between equimolar amounts of PtCl2(diene) and Me3SnR in dichloromethane. Most reactions also gave some of the corresponding PtR2(diene) complex, which was readily separated by chromatography, and Pt(p-MeOC6F4)2(nbd)

  配合物PTCl（diene）R（二烯=六-1,5-二烯（hex）或降冰片二烯（nbd），R C 6 F 5，p -HC 6 F 4或p -MeOC 6 F 4 ;二烯通过在二氯甲烷中等摩尔量的PTCl 2（二烯）和Me 3 SnR之间的反应制备二烯＝二烯＝二环戊二烯（dcy），R ＝ C 6 F 5）。大多数反应还产生了一些相应的PTR 2（二烯）配合物，该配合物很容易通过色谱法进行分离，还生成了PT（p -MeOC 6 F 4）2当使用摩尔比时，从PTCl 2（nbd）和Me 3 Sn（p -MeOC 6 F 4）以高收率获得（nbd）。尝试制备氯铂酸（DCY）R（R p -HC 6 ˚F 4或p -MeOC 6 ˚F 4）选自Me 3 SNR仅给出PTR 2（DCY）在沸腾的CH 2氯2尽管使用的反应物的化学计量，和的PT（p -MeOC 6 ˚F 4）2（DCY）或无反应（R p
• Heterogeneous, platinum-catalyzed hydrogenation of (diolefin)dialkylplatinum(II) complexes: kinetics
  作者：Timothy M. Miller、Alan N. Izumi、Yen Shiang. Shih、George M. Whitesides

  DOI：10.1021/ja00218a024

  日期：1988.5

  isotope effect: nu/sub H/sub 2//nu/sub D/sub 2// approx. = 1.0. Examination of the relative ratesmore » of reaction of a series of (diolefin)dialkylplatinum(II) complexes indicates that the structure of the diolefin has a greater influence on the rate of reaction than does that of the alkyl group. Competitive experiments show that rates are influenced by adsorption of the (Ol/sub 2/)PtR/sub 2/ complex to

  (二烯烃)二烷基铂(II)配合物((Ol/sub 2/)PtR/sub 2/)在铂黑催化剂存在下被二氢迅速还原：有机基团转化为烷烃，铂(II)转化为铂金(0)。该铂(0)结合到铂黑催化剂的表面中。该反应是由铂 (0) 催化的多相过程。其速率受传质和催化剂表面积的强烈影响。它被二新戊基汞、二正辛基硫醚和三叔丁基膦中毒。由于催化剂表面通过铂的沉积不断更新，然而，与更熟悉的铂催化反应（如烯烃加氢）相比，该反应对中毒的敏感性较低。观察到的减少 (1, 5-环辛二烯）二甲基铂（II）取决于反应条件。观察到两个限制动力学机制。一方面，二氢向催化剂表面的传质是限速的；第二，铂表面上发生的反应是限速的。传质受限状态下反应的活化能约为 3 kcalmol 并且在反应速率限制方案中大约为 3 kcalmol。15 大卡摩尔。在这两种情况下都没有动力学同位素效应：nu/sub H/sub 2//nu/sub D/sub
• In-plane coordinated double bonds. Molecular structures, spectroscopy, and stability of 5-methylenecyclooctene and 5-methylenecycloheptene complexes of platinum(II)
  作者：Margaret H. Rakowsky、John C. Woolcock、Laura L. Wright、David B. Green、Michael F. Rettig、Richard M. Wing

  DOI：10.1021/om00149a015

  日期：1987.6.1
• Reactions of di-2-pyridyl sulfide with the palladium(II) and platinum(II) diene or methoxydiene complexes. Dynamic behaviour of the cationic compounds. Crystal structure of Pd(di-2-pyridyl sulfide)Cl2
  作者：Giuseppe Tresoldi、Enrico Rotondo、Pasquale Piraino、Maurizio Lanfranchi、Antonio Tiripicchio

  DOI：10.1016/s0020-1693(00)82668-7

  日期：1992.4

  The complexes [M(dps)Cl2] (M = Pd(II) (1); Pt(II) (2)) and the labile compounds [M(MeOdiene)(dps)Cl] (M = Pd(II), MeOdiene = CH3OC8H12 (3) or CH3OC10H12 (4); M = Pt(II), MeOdiene = CH3OC8H12 (5) or CH3OC10H12 (6)) have been synthesized by reaction of dps (dps = di-2-pyridyl sulfide) with [M(diene)Cl2] (diene = cycloocta-1,5-diene or dicyclopentadiene) and the appropriate chloro-bridged methoxydiene complexes, respectively. The last reactions required drastic conditions. Also the reactions of dps with the solvento species [M(diene)(acetone)2]X2 and [M(MeOdiene)(acetone)2]X (X = BF4, PF6, ClO4) have been studied and the compounds [M(MeOdiene)(dps)]X (M = Pd(II), MeOdiene = CH3OC8H12 (7) or CH3OC10H12 (8); M = Pt(II), MeOdiene = CH3OC8H12 (9) or CH3OC10H12 (10)) were prepared. The structure of 1 has been determined by X-ray diffraction methods. Crystals are monoclinic, space group P2(1)/n, with Z = 4 in a unit cell of dimensions a = 9.933(4), b = 14.802(5), c = 8.465(3) angstrom, beta = 101.94(2)-degrees. The structure has been solved from diffractometer data by Patterson and Fourier methods and refined by full-matrix least-squares on the basis of 2163 observed reflections to R and R' values of 0.0277 and 0.0348, respectively. In the square planar coordination around the Pd atom the dps molecule acts as a chelate ligand through the two pyridinic N atoms and adopts a N,N-inside conformation. The six-membered chelate ring shows a boat conformation with the Pd and S atoms out of the plane through the other four atoms on the same side. Although dissociation in the usual solvents prevents full characterization of 3-6 IR spectra suggest that the dps acts as monodentate ligand. The H-1 NMR spectra, at variable temperature, and C-13 NMR spectra of 7-10 show that the cationic complexes in solution undergo at least two dynamic processes; a ligand site exchange and a boat to boat inversion of the chelate dps ring. The ligand site exchange is fast, in the NMR time scale, at room temperature for palladium complexes and at higher temperature for the platinum complexes and makes equivalent the pyridine rings of dps. This process is interpreted in terms of formation of stereochemically non-rigid five-coordinate intermediates. The boat to boat inversion is fast at room temperature at least for platinum complexes. At low temperature the latter process is absent or occurs at markedly reduced rate for palladium complexes while the slow ligand site exchange results in equilibria between two conformers.