trans-[PtCl4(PhCN)2] | 116126-94-4

• 英文名称: trans-[PtCl4(PhCN)2]
• 英文别名: trans-[PtCl₄(PhCN)₂]；trans-[PtCl4(benzonitrile)2]；trans-[PtCl4(NCPh)2]
• CAS: 116126-94-4；97175-95-6
• 化学式: C₁₄H₁₀Cl₄N₂Pt
• 分子量: 543.139
• InChiKey: LVTBWWVLLTXOEV-UHFFFAOYSA-J

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

反应信息

• 作为反应物：
  描述：

  dimethyl ammonium azide 、 trans-[PtCl4(PhCN)2] 以 二氯甲烷 为溶剂， 以69%的产率得到trans-[PtCl4(CN4Ph)2][Me2NH2]2
  参考文献：
  名称：

  A new route to N(1)-5R-tetrazole complexes via azidation to nitriles coordinated to Pt(II) and Pt(IV)

  摘要：

  New tetrazolate complexes trans-[PtCl2(RCN4)(2)](2), trans-[PtCl4(RCN4)(2)](2) with Ph3PCH2Ph+ and (CH3)(2)NH2+ counterions have been obtained by azidation of nitriles coordinated to Pt(II) and Pt(IV) {trans-[PtCl2(RCN)(2)] and trans-[PtCl4(RCN)(2)] (R = Et, Ph)} and characterized. The composition and the molecular structure of the complexes obtained were established by the CHN elemental analyses, H-1 and C-13 NMR spectroscopy, IR spectroscopy, mass spectrometry, and X-ray diffraction. The coordination of nitriles to Pt(II) and Pt(IV) is shown significantly activate the azidation: the reaction proceeds with a higher rate and at relatively low temperature compared with the classical 1,3-dipolar addition of azides to nitriles. (C) 2011 Elsevier B.V. All rights reserved.

  DOI：

  10.1016/j.ica.2011.05.011
• 作为产物：
  描述：

  bis(benzonitrile)dichloroplatinum(II) 以 not given 为溶剂， 生成 trans-[PtCl4(PhCN)2]
  参考文献：
  名称：

  Nucleophilic addition of bifunctional sulfimidosulfides to platinum(IV)-coordinated nitriles

  摘要：

  铂(IV)腈络合物[PtCl4(RCN)2] (R = Me, CH2Ph, Ph)与1,2-和1,4-PhS(=NH)C6H4SPh在CH2Cl2中反应，得到硫酰亚胺和配位化合物的加成产物腈，即 [PtCl4{NH=C(R)N=S(Ph)(C6H4SPh)}2] 配合物。后者的分离产率为 75-90%，并通过元素分析、正离子 FAB 质谱、红外光谱以及 1H 和 13C1H NMR 光谱进行表征。在 +40 至 -70 °C 的温度范围内研究的 CD2Cl2 中模型 [PtCl4{NH=C(R)N=SPh2}2] 配合物 (R = Me, Et) 的 1H NMR 光谱的温度依赖性配体的E—Z异构化是+40至-10°C范围内的动态过程。计算了该过程的活化自由能。

  DOI：

  10.1007/s11172-005-0017-x

文献信息

• Direct Addition of Alcohols to Organonitriles Activated by Ligation to a Platinum(IV) Center
  作者：Nadezhda A. Bokach、Vadim Yu. Kukushkin、Maxim L. Kuznetsov、Dmitrii A. Garnovskii、Giovanni Natile、Armando J. L. Pombeiro

  DOI：10.1021/ic011025h

  日期：2002.4.1

  effect. X-ray structure determinations were performed for trans-[PtCl(4)[(E)-NH=C(Me)OEt](2)] (2), trans-[PtCl(4)[(E)-NH=C(Et)OEt](2)] (10), trans-[PtCl(4)[(E)-NH=C(Et)OPr-i](2)] (11), trans-[PtCl(4)[(E)-NH=C(Et)OPr-n](2)] (12), and cis-[PtCl(4)[(E)-NH=C(Et)OMe](2)] (14). Ab initio calculations have shown that the EE isomers are the most stable ones for both platinum(II) and platinum(IV) complexes, whereas

  在45度下用R'OH（R'= Me，Et，n-Pr，i-Pr，n-Bu）处理反式[PtCl（4）（RCN）（​​2）]（R = Me，Et） C在所有情况下都允许分离反-[PtCl（4）[（E）-NH = C（R）OR']（2）]亚氨基酯配合物，而顺式-[PtCl（4）（ RCN）（​​2）]和空间位阻最小的醇（甲醇和乙醇）导致形成顺式[PtCl（4）[（E）-NH = C（R）OR']（2）]（R / R'= Me / Me）或反式-[PtCl（4）[（E）-NH = C（Et）OR']（2）]（R'= Me，Et），后者是通过热异构化形成的（ ROH，回流，最初形成的相应顺式异构体的3小时）。醇R'OH与顺式[PtCl（4）（RCN）（​​2）]之间的反应（R = Me，R'= Et，n-Pr，i-Pr，n-Bu; R = Et; R' = n-Pr，i-Pr，n-Bu），表现出更大的R
• Formation of two stable seven-membered chelate rings bound to one metal center due to addition of bifunctional amine to coordinated nitriles
  作者：Yuri N. Kukushkin、Natalya P. Kiseleva、Ennio Zangrando、Vadim Yu. Kukushkin

  DOI：10.1016/s0020-1693(98)00337-5

  日期：1999.2

  was also obtained upon treatment of the platinum(IV) complex [PtCl4(PhCN)2] with ethylenediamine in the same reaction conditions. The X-ray diffraction analysis performed on a single crystal having formulation [Pt(NHC(Ph)NHCH2CH2NH2)2](SbF6)2 showed that the complex ion contains two unusual seven-membered organic metallacycles bound to the same platinum(II) center.

  摘要顺式和反式[PtCl2（PhCN）2]与三当量的乙二胺在水中的反应导致分离出以双水合物形式分离的[Pt（NHC（Ph）NHCH2CH2NH2）2] Cl2。该配合物与NaPF6或KSbF6在水溶液中的易位反应导致生成适当的[Pt（NHC（Ph）NHCH2CH2NH2）2] X2·nH2O [X = PF6; n = 3；X = SbF6; n = 2]盐。在相同的反应条件下，用乙二胺处理铂（IV）配合物[PtCl4（PhCN）2]，也可以获得二水合物[Pt（NH = C（Ph）NHCH2CH2NH2）2Cl2·2H2O。对具有[Pt（NHC（Ph）NHCH2CH2NH2）2]（SbF6）2组成的单晶进行的X射线衍射分析表明，该复合离子包含两个与同一铂（II）结合的不寻常的七元有机金属环） 中央。
• Iminoacylation. 3. Formation of Platinum(IV)-Based Metallaligands Due to Facile One-End Addition of <i>v</i><i>ic</i>-Dioximes to Coordinated Organonitriles^1-3
  作者：Vadim Yu. Kukushkin、Tatyana B. Pakhomova、Nadezhda A. Bokach、Gabriele Wagner、Maxim L. Kuznetsov、Mathea Sophia Galanski、Armando J. L. Pombeiro

  DOI：10.1021/ic990552m

  日期：2000.1.24

  [PtCl4(NH=C(Me)ON=C[C4Hs]C=NOH)2] (4) was isolated exclusively in cis configuration with the two metallaligand "arms" held together by intramolecular hydrogen bonding between the two peripheral OH groups, as it was proved by single-crystal X-ray diffractometry. The classic substitution products, e.g. [PtC12(N,N-dioximato)2] (12-15), are formed in the addition reaction as only byproducts in minor yield;

  vic-dioximes 与有机腈铂 (IV) 配合物 trans-[PtCl4(RCN)2] 的反应 (R = Me, CH2Ph, Ph, vic-dioxime = 二甲基乙二肟；R = Me, vic-dioxime = cyclohexa-, cyclohepta - 和环辛二酮二肟）在相对温和的条件下快速进行，并提供二肟与腈碳的一端加成产物，即 [PtC4(NH=C(R)ON=[spacer]=NOH)2] (1 -6) (R = Me, CH2Ph, Ph, 间隔基 = C(Me)C-(Me) 用于二甲基乙二肟；R = Me, 间隔基 = C[C4H8]C, C[C5H10]C, C[C6H12]C 用于其他二肟），产生一种新型的金属配体。所有加成化合物均通过元素分析（C、H、N、C1、Pt）、FAB 质谱以及 IR 和 1H、13C[1H] 和 195Pt NMR 光谱进行表征。二甲基甲酰胺双溶剂化物
• One-end nucleophilic addition of di- and triamines to PtIV-coordinated nitriles as an entry to (amidine)PtIV complexes bearing pendant NH2-groups
  作者：Nadezhda A. Bokach、Nina P. Konovalova、Yu Wang、Yulia E. Moskalenko、Alexander V. Gribanov、Vadim Yu. Kukushkin

  DOI：10.1039/c001103g

  日期：——

  The reactions of trans-[PtCl4(RCN)2] (R = Me, Et, CH2Ph, Ph) with the diamines and the triamine NH2spacer}NH2 (spacer = CH2CH2, CH(Me)CH2, CH2CH2CH2, CH2CH2CH2CH2, CH2CH2NHCH2CH2) in a molar ratio 1 : 2 produce trans-[PtCl4NHC(R)NHspacer}NH2}2] (spacer/R = CH2CH2/Et 1, CH2CHMe/Et 2 (a mixture of regioisomers), CH2CH2CH2/Et 3, CH2CH2CH2CH2/Et 4, CH2CH2/Me 5, CH2CH2/CH2Ph 6, CH2CH2/Ph 7, CH2CH2NHCH2CH2/Et 8) with the monodentately coordinated amidine ligands having the pendant NH2 groups. The complexes have been characterised by C, H, and N elemental analyses, 13C CP-MAS NMR and IR spectroscopy, (TOF)-ESI-MS, and [1·H2](Pic)2·EtOH also by X-ray diffraction.

  反式-[PtCl4(RCN)2]（R = Me、Et、 Ph、Ph）与二胺和三胺 NH2间隔物}NH2（间隔物 = 、CH(Me)CH2、 、 、 NH ）以摩尔比 1 ： 2 的摩尔比生成反式-[PtCl4NHC(R)NH间隔物}NH2}2]（间隔物/R = /Et 1、 CHMe/Et 2（区域异构体混合物）、 /Et 3、 /Et 4、 /Me 5、 / Ph 6、 /Ph 7、 NH /Et 8），单端配位的脒配体具有悬垂的 NH2 基团。这些配合物的特征已通过 C、H 和 N 元素分析、13C CP-MAS NMR 和 IR 光谱、（TOF）-ESI-MS 以及 [1-H2](Pic)2-EtOH X 射线衍射测定。
• The first examples of metal-mediated addition of a phosphorus imine to nitriles; the preparation and X-ray crystal structures of [PtCl₄{NHC(Et)NPPh₃}₂] and [PtCl₂(EtCN){NHC(Et)NPPh₃}]
  作者：Nadezhda A. Bokach、Vadim Yu. Kukushkin、Paul F. Kelly、Matti Haukka、Armando J. L. Pombeiro

  DOI：10.1039/b502970h

  日期：——

  Imino(triphenyl)phosphorane, Ph3P=NH (1), reacts with nitrile complexes of Pt(IV) to generate hydrolytically sensitive [PtCl4NH=C(R)N=PPh3}2](R=Me 2a, Et 2b, Ph 2c), and with the Pt(II) complex [PtCl2(EtCN)2] to give [PtCl2(EtCN)NH=C(Et)N=PPh3}](3) and [PtCl2NH=C(Et)N=PPh3}2](4); X-ray crystallography performed upon (2b) and (3) confirms the presence of an imine/nitrile addition ligand bound by the terminal

  亚氨基（三苯基）磷烷Ph3P = NH（1）与Pt（IV）的腈络合物反应生成水解敏感的[PtCl4 NH = C（R）N = PPh3} 2]（R = Me 2a，Et 2b， Ph 2c），并与Pt（II）配合物[PtCl2（EtCN）2]生成[PtCl2（EtCN）NH = C（Et）N = PPh3}]（3）和[PtCl2 NH = C（Et ）N = PPh3} 2]（4）; 对（2b）和（3）进行的X射线晶体学证实，存在被末端氮结合的亚胺/腈加成配体。