cis-dichlorobis(propiononitrile)platinum(II) | 146143-88-6

• 分子结构分类: 有机化合物 - 有机氮化合物
• 英文名称: cis-dichlorobis(propiononitrile)platinum(II)
• 英文别名: cis-[PtCl₂(NCEt)₂]；cis-[PtCl₂(EtCN)₂]；Dichloroplatinum;propanenitrile；dichloroplatinum;propanenitrile
• CAS: 146143-88-6
• 化学式: C₆H₁₀Cl₂N₂Pt
• 分子量: 376.145
• InChiKey: LAOHIQKBVVOEKN-UHFFFAOYSA-L

计算性质

• 辛醇/水分配系数(LogP)：
  3.22
• 重原子数：
  11
• 可旋转键数：
  0
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.67
• 拓扑面积：
  47.6
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  cis-dichlorobis(propiononitrile)platinum(II) 在 KOH 、 MeOH 作用下， 以 甲醇 为溶剂， 以95%的产率得到cis-[PtCl2(E-HN=C(OMe)Et)2]
  参考文献：
  名称：

  Cini, Renzo; Caputo, Paola A.; Intini, Francesco P., Inorganic Chemistry, 1995, vol. 34, # 5, p. 1130 - 1137

  摘要：

  DOI：
• 作为产物：
  描述：

  cis-[PtCl2(2-Et-5,5,6,6-tetramethyl-3a,4,5,6-tetrahydroimidazo[1,2-b][1,2,4]oxadiazole)2] 以 氘代氯仿 为溶剂， 生成 cis-dichlorobis(propiononitrile)platinum(II)
  参考文献：
  名称：

  铂金（II）金属介导的1，3-偶极环加成反应生成的络合四氢咪唑并[1,2- b ] [1,2,4]恶二唑。没有金属中心就不会存在的新型杂环

  摘要：

  一种新型的杂环配体，即2- R -3a-R'-5,5,6,6-四甲基-3a，4,5,6-四氢咪唑[1,2- b ] [1,2， 4]恶二唑是由分子间Pt II介导的咪唑啉N-氧化物O NC（R'）NH CMe 2 CMe 2（R'= H，Me）与配位腈之间的分子间介导的1,3-偶极环加成反应生成的。顺式和反式[PtCl 2（RCN）2 ]复合体（R = NMe 2，NC 5 H 10，Et）。反应在温和的条件下（CH 2 Cl 2，20-25°C，0.5-3 h），得到络合物[PtCl 2 { N═C（R）O NC（R'）NH CMe 2 CMe 2 } 2 ]（R / R'= NMe 2 / Me ，顺式和反式1； NMe 2 / H，顺式和反式2； R / R'= N（C 5 H 10）/ Me，顺式和反式3； N（C 5 H 10）/ H，顺式和反式4； Et / H，顺式和反式5）

  DOI：

  10.1021/om800963d

文献信息

• Dramatically Enhanced Solubility of Halide-Containing Organometallic Species in Diiodomethane: The Role of Solvent⋅⋅⋅Complex Halogen Bonding
  作者：Mikhail A. Kinzhalov、Mariya V. Kashina、Alexander S. Mikherdov、Ekaterina A. Mozheeva、Alexander S. Novikov、Andrey S. Smirnov、Daniil M. Ivanov、Mariya A. Kryukova、Aleksandr Yu. Ivanov、Sergej N. Smirnov、Vadim Yu. Kukushkin、Konstantin V. Luzyanin

  DOI：10.1002/anie.201807642

  日期：2018.9.24

  σ‐hole‐donating ability of this solvent, which results in the formation of uniquely strong solvent–(metal complex) halogen bonding. The strength of the halogen bonding is attenuated by the introduction of additional halogen atoms in the organometallic species owing to the competitive formation of more favourable intermolecular complex–complex halogen bonding. The exceptional solvation properties of diiodomethane

  在当前的研究中，我们评估了许多有机金属物种的溶解度，并表明与其他卤代烷烃溶剂相比，二碘甲烷中的溶解度得到了显着提高。CH 2 I 2的更好的溶剂化性能与这种溶剂的σ空穴提供能力强得多有关，这导致形成独特的牢固的溶剂-（金属络合物）卤素键。由于竞争性形成了更有利的分子间配合物-配合物卤素键，竞争性形成了有机金属物种中引入的其他卤素原子，从而削弱了卤素键的强度。二碘甲烷的出色溶剂化特性及其对有机金属物种的惰性使该溶剂成为NMR研究（特别是不敏感自旋光谱的获取）的良好候选者。
• Synthesis of Platinum(II) Phoshine Isocyanide Complexes and Study of Their Stability in Isomerization and Ligand Disproportionation Reactions
  作者：M. A. Kinzhalov、M. V. Kashina、A. S. Mikherdov、S. A. Katkova、V. V. Suslonov

  DOI：10.1134/s107036321806021x

  日期：2018.6

  1H NMR, COSY, NOESY, HSQC, and HMBC spectroscopy, and X-ray diffraction analysis. The solid-state and solution structures of the complexes and their stability in isomerization and ligand disproportionation reactions were studied.

  合成了异硫氰酸膦异氰酸酯与顺丁烯二异氰化物和膦配体的顺式[[PtCl 2（CNMes）（P）]]，产率为92％至98％。通过质谱，IR和1 H NMR，COSY，NOESY，HSQC和HMBC光谱以及X射线衍射分析对产物进行表征。研究了配合物的固态和溶液结构及其在异构化和配体歧化反应中的稳定性。
• Synthesis of Mixed-Ligand Nitrileand Carbonyl–Isocyanide Complexes of Platinum(II) and Their Reaction with P-Toluenesulfonyl Hydrazide
  作者：R. A. Popov、A. S. Novikov、A. S. Mikherdov

  DOI：10.1134/s1070363218110166

  日期：2018.11

  2,6-Me2C6H3) have been prepared for the first time. The compounds have been characterized by mass spectrometry, IR and NMR spectroscopy. Reactivity of the prepared complexes towards N-nucleophiles has been studied using the reaction with p-toluenesulfonyl hydrazide as the example.

  铂（II）反-[PtCl 2（NCEt）CNXyl]和反-[PtCl 2（CO）CNXyl]（Xyl = 2,6-Me 2 C 6 H 3）的混合配体腈和羰基异氰化物配合物第一次准备。该化合物已经通过质谱，IR和NMR光谱表征。以与对甲苯磺酰肼的反应为例，研究了制备的配合物对N-亲核试剂的反应性。
• Synthesis and study of Pt(II)–nitrile complexes. Multinuclear NMR spectra and crystal structures of compounds of the types [Pt(R-CN)Cl₃]⁻ and <i>cis</i> and <i>trans</i>-Pt(R-CN)₂Cl₂
  作者：Fernande D. Rochon、Robert Melanson、Eryk Thouin、Corinne Bensimon、André L. Beauchamp

  DOI：10.1139/v96-018

  日期：1996.2.1

  Complexes of the type [Pt(R-CN)Cl₃]⁻ were synthesized and studied by ¹H, ¹³C, and ¹⁹⁵Pt NMR spectroscopies. The ²J(¹⁹⁵Pt-¹³C) coupling constants are about 240 Hz. The signals due to the cyano carbon atoms of the coordinated ligands were observed at higher fields than those of the free ligands. The shielding on the cyano carbon increases as the alkyl chain lengthens and also when the branching increases. The ¹⁹⁵Pt signals of all the complexes were observed around −2000 ppm. The crystal structures of (NMe₄)[Pt(C₃H₇-CN)Cl₃] (1) and (NMe₄)[Pt(p-HO-C₆H₄-CN)Cl₃] (2) were determined. Compound 1 is monoclinic, P2₁/c, a = 8.384(5), b = 15.336(19), c = 11.759(9) Å, β = 99.52(6)°, Z = 4, R = 0.054, and wR = 0.051. Crystal 2 is tetragonal with a = 16.222(6), c = 12.052(5) Å, Z = 8, R = 0.059, and wR = 0.044. The Pt—CL bond trans to the nitrile ligand is shorter than normal (2.276(3) Å for 1 and 2.264(7) Å for 2) while the two other bonds are normal (2.293(4), 2.287(3) Å for 1 and 2.320(7), 2.275(8) Å for 2). The Pt—N bonds are 1.97(1) Å (1) and 1.92(2) Å (2) and the segments Pt-N≡C-C are linear. Disubstituted compounds were also synthesized and studied by multinuclear NMR. The ¹⁹⁵Pt signals of the cis isomers were observed at lower fields than those of the trans isomers (Δ ≈ 65 ppm), while the ¹³C signals of the cyano carbons of the trans isomers were observed at lower fields than those of the cis compounds (Δ ≈ 0.6 ppm). The cis complexes isomerize to the trans compounds upon heating. The crystal structures of cis-(3) and trans-Pt(C₂H₅-CN)₂Cl₂ (4) and also of cis-Pt(p-HO-C₆H₄-CN)₂Cl₂ (5) were determined. Crystal 3 is monoclinic, P2₁/c, a = 7.506(5), b = 9.539(5), c = 14.823(7) Å, β = 92.31(4)°, Z = 4, R = 0.050, and wR = 0.042. The trans isomer 4 is monoclinic with the Pt atom on an inversion centre, P2₁/c, a = 5.149(4), b = 9.394(8), c = 10.944(10) Å, β = 97.84(7)°, Z = 4, R = 0.017 and wR = 0.020. Finally, compound 5 is triclinic, P-1, a = 7.464(3), b = 10.712(6), c = 12.291(5) Å, α = 75.63(4)°, β = 75.63(4)°, γ = 80.32(4)°, Z = 2, R = 0.045, and wR = 0.056. The Pt—Cl bond distances for the cis isomers are 2.269(5), 2.270(4) Å for 3 and 2.274(2), 2.279(3) Å for 5 while they are 2.289(3) Å for the trans isomer (4). The Pt—N bonds are 1.962(14), 1.988(11) Å (3), 1.972(7), 1.976(7) Å (5) and 1.969(5) Å for 4. Key words: platinum, nitrile, NMR, isomerization, crystal structure.

  以[Pt(R-CN)Cl3]−类型的配合物通过1H、13C和195Pt核磁共振光谱合成和研究。2J(195Pt-13C)偶合常数约为240 Hz。配体的氰基碳原子的信号在比自由配体更高的场强处被观察到。随着烷基链长度的增加以及分支的增加，氰基碳的屏蔽增加。所有配合物的195Pt信号观察到约在-2000 ppm附近。确定了(NMe4)[Pt(C3H7-CN)Cl3] (1) 和 (NMe4)[Pt(p-HO-C6H4-CN)Cl3] (2) 的晶体结构。化合物1为单斜晶系，P21/c，a = 8.384(5) Å，b = 15.336(19) Å，c = 11.759(9) Å，β = 99.52(6)°，Z = 4，R = 0.054，wR = 0.051。晶体2为四方晶系，a = 16.222(6) Å，c = 12.052(5) Å，Z = 8，R = 0.059，wR = 0.044。与腈配体相对的Pt—Cl键长度较正常短（1为2.276(3) Å，2为2.264(7) Å），而另外两个键长度正常（1为2.293(4)、2.287(3) Å，2为2.320(7)、2.275(8) Å）。Pt—N键为1.97(1) Å（1）和1.92(2) Å（2），Pt-N≡C-C段为线性。还合成了和通过多核NMR研究了二取代化合物。顺式异构体的195Pt信号观察到比反式异构体更低的场强（Δ约65 ppm），而反式异构体的氰基碳13C信号观察到比顺式化合物更低的场强（Δ约0.6 ppm）。顺式配合物在加热时异构为反式化合物。确定了顺式-(3) 和 反式-Pt(C2H5-CN)2Cl2 (4) 以及顺式-Pt(p-HO-C6H4-CN)2Cl2 (5) 的晶体结构。晶体3为单斜晶系，P21/c，a = 7.506(5) Å，b = 9.539(5) Å，c = 14.823(7) Å，β = 92.31(4)°，Z = 4，R = 0.050，wR = 0.042。反式异构体4为单斜晶系，Pt原子处于反转中心，P21/c，a = 5.149(4) Å，b = 9.394(8) Å，c = 10.944(10) Å，β = 97.84(7)°，Z = 4，R = 0.017，wR = 0.020。最后，化合物5为三斜晶系，P-1，a = 7.464(3) Å，b = 10.712(6) Å，c = 12.291(5) Å，α = 75.63(4)°，β = 75.63(4)°，γ = 80.32(4)°，Z = 2，R = 0.045，wR = 0.056。顺式异构体的Pt—Cl键距离为2.269(5)、2.270(4) Å（3）和2.274(2)、2.279(3) Å（5），而反式异构体为2.289(3) Å（4）。Pt—N键为1.962(14)、1.988(11) Å（3），1.972(7)、1.976(7) Å（5）和1.969(5) Å（4）。关键词：铂，腈，核磁共振，异构化，晶体结构。
• Synthesis and spectroscopic investigation of cis and trans isomers of bis(nitrile)dichloroplatinum(II) complexes
  作者：Daniela Fraccarollo、Roberta Bertani、Mirto Mozzon、Umberto Belluco、Rino A. Michelin

  DOI：10.1016/s0020-1693(00)84996-8

  日期：1992.11

  Abstract A series of bis(nitrile) complexes cis- and trans-Cl2Pt(NCR)2(R=C6H5,p-CH3C6H4, p-CF3C6H4, o-CH3C6H4,CH3, CH3CH2, CH3CH2CH2, (CH3)2CH, (CH3)3C) has been prepared by either one of the two methods, K2PtCl4/H2O/ RCN(excess) or PtCl2/RCN(neat), both of which usually yield the nitrile complexes as a mixture of cis and trans isomers in different ratios depending on the experimental conditions such

  摘要一系列双（腈）配合物顺式和反式Cl2Pt（NCR）2（R = C6H5，p-CH3C6H4，p-CF3C6H4，o-CH3C6H4，CH3，CH3CH2，CH3CH2CH2，（CH3）2CH，（CH3） 3C）是通过以下两种方法之一制备的：K2PtCl4 / H2O / RCN（过量）或PtCl2 / RCN（纯净），这两种方法通常会生成顺式和反式异构体混合物的腈络合物，其比例不同，取决于实验条件如反应温度和反应时间。通过利用反式物质在非极性溶剂中通常较高的溶解度，可以通过分步结晶来分离每种双（腈）化合物的立体异构体。通过IR，1 H和13 C NMR光谱学表征该配合物。