trans-[PtCl4(propiononitrile)2] | 92275-25-7

• 分子结构分类: 有机化合物 - 有机氮化合物
• 英文名称: trans-[PtCl4(propiononitrile)2]
• 英文别名: trans-[PtCl4(EtCN)2]；platinum(4+);propanenitrile;tetrachloride
• CAS: 92275-25-7
• 化学式: C₆H₁₀Cl₄N₂Pt
• 分子量: 447.051
• InChiKey: QZJRKZZGHYFGMR-UHFFFAOYSA-J

计算性质

• 辛醇/水分配系数(LogP)：
  4.6
• 重原子数：
  13
• 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：

  水杨基羟肟酸 、 trans-[PtCl4(propiononitrile)2] 以 二氯甲烷 为溶剂， 生成 trans-[PtCl4(NH=C(Et)ON=C(OH)C6H4OH-o)2]
  参考文献：
  名称：

  Novel Reactivity Mode of Hydroxamic Acids:  A Metalla-Pinner Reaction

  摘要：

  The reaction between the nitrile complex trans-[PtCl4(EtCN)(2)] and benzohydroxamic acids RC6H4C(=O)NHOH (R = p-MeO, p-Me, H, p-Cl, o-HO) proceeds smoothly in CH2Cl2 at similar to45degreesC for 2-3 h (sealed tube) or under focused 300 W microwave irradiation for similar to15 min at 50degreesC giving, after workup, good yields of the imino complexes [PtCl4 {NH=C(Et)ON=C(OH)(C6H4R)}(2)] which derived from a novel metalla-Pinner reaction. The complexes [PtCl4{NH=C(Et)oN=C(OH)(C6H4R)}(2)] were characterized by elemental analyses (C, H, N), FAB mass spectrometry, and IR and H-1 and C-13{H-1} spectroscopies, and [PtCl4{NH=C(Et)ON=C(OH)(Ph)}(2)] (as the bis-dimethyl sulfoxide solvate), by X-ray single-crystal diffraction. The latter disclosed its overall trans-configuration with the iminoacyl species in the hydroximic tautomeric form in E-configuration which is held by N-H...N hydrogen bond between the imine =NH atom and the hydroximic N atom.

  DOI：

  10.1021/ic025554c
• 作为产物：
  描述：

  氯 、 trans-[PtCl₂(EtCN)2] 以 氯仿 为溶剂， 以80%的产率得到trans-[PtCl4(propiononitrile)2]
  参考文献：
  名称：

  铂（IV）介导的腈水解产生金属结合的亚氨基

  摘要：

  铂（IV）配合物顺/反-[PtCl 4（MeCN）2 ]和反-[PtCl 4（EtCN）2 ]可以在温和条件下平稳地与水，包含在非干燥的商业广告中 丙酮，得到反式-[PtCl 4 {N（H）C（OH）Me} 2 ]·Me 2 CO（1）或反式-[PtCl 4 {N（H）C（OH）Et} 2 ]（2） ; 与相关的铂（II）体系相比，不需要氢氧化物来提供与金属结合的金属羧酰胺以亚氨基形式稳定。在非干燥丙酮，反式-[PtCl 4（EtCN）2 ]和MeC（O）NH 2之间的反应得到1（源自取代基）和2（源自水解）的混合物，而未干燥二氯甲烷顺式-[PtCl 4 {N（H）C（OH）Me} 2 ]和顺式-[PtCl 4 {N（H）C（OH）Et} 2 ]的同构混合物，即顺式-[PtCl 4 { Z获得-N（H）C（OH）Me} 2 ] 0.66 ·顺式-[PtCl 4 { Z -N（H）C（OH）Et}

  DOI：

  10.1039/b108327a

文献信息

• Regioselective HON-addition of bifunctional hydrazone oximes to Pt(iv)-bound nitrilesDedicated to Professor Ilya I. Moiseev on the occasion of his 75th birthday.
  作者：Dmitrii A. Garnovskii、Armando J. L. Pombeiro、Matti Haukka、Piotr Sobota、Vadim Yu. Kukushkin

  DOI：10.1039/b402105c

  日期：——

  brings about the formation of the platinum(II) complexes trans-[PtCl2NHC(Et)ONC(Me)C(Ph)NNCH(C6H3-2-OH-5-NO2}2] (5) and trans-[PtCl2NHC(Et)ONC(Me)C(Ph)NNCH(C6H4-4-NO2}2] (6), respectively, containing functionalized remote peripherical groups. Metallization of 5, which can be considered as a novel type of metallaligand, was achieved by its reaction with M(OAc)2·nH2O (M = Cu, n = 2; M = Co, n = 4) in a

  45肟MeC（NOH）C（R'）NNH 2（R'= Me，Ph）在45°C的CH 2 Cl中处理反式-[PtCl 4（RCN）2 ]（R = Me，Et）2导致反式-[PtCl 4 NH C（R）ON C（Me）C（R'）NNH 2 } 2 ]的形成（R / R'= Me / Ph 1，Et / Me 2，Et / Ph 3）是由于双官能团MeC（NOH）C（R'）NNH 2在腈基上的区域选择性OH加成。3与Ph的反应3 PCHCO 2 Me可以形成Pt（ II）配合物反式-[PtCl 2 NHC（Et）ONC（Me）C（Ph）NNH 2 } 2 ]（ 4）。在4中，通过用CDCl 3中的2当量的双（1,2-二苯基膦基）乙烷（dppe）取代而释放出亚胺配体，以与游离配体一起得到固体[Pt（dppe） 2 ] Cl 2。寿命有限的游离亚氨基酰基hydr在20–25°C下约20小时内分解为母体有机腈和hydr肟。游离NH
• Platinum(<scp>iv</scp>)-mediated coupling of dione monoximes and nitriles: a novel reactivity pattern of the classic oxime-based chelating ligands
  作者：Anastassiya V. Makarycheva-Mikhailova、Matti Haukka、Nadezhda A. Bokach、Dmitrii A. Garnovskii、Mathea S. Galanski、Bernhard K. Keppler、Armando J. L. Pombeiro、Vadim Yu. Kukushkin

  DOI：10.1039/b202947b

  日期：——

  The reaction between dione monoximes and platinum(iv) nitrile complexes leads, instead of the conventional substitution, to metal-mediated coupling, giving iminoacylated species which, on being liberated, undergo disintegration to the nitrile and the oxime.

  双酮一氧胺与铂（IV）氰基配合物之间的反应，不是传统的取代反应，而是通过金属介导偶联反应，形成酰化亚胺物种，当其被释放时，会发生分解生成氰基和肟基。
• 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
• Synthesis of amidine complexes by metal-mediated addition of amino acid esters to coordinated nitriles
  作者：A. V. Makarycheva-Mikhailova、E. A. Tronova、V. Yu. Kukushkin

  DOI：10.1007/s11172-005-0330-4

  日期：2005.3

  The reaction of the nitrile platinum(IV) complex trans-[PtCl4(EtCN)2] with amino acid esters H2NC(R1)(R2)CO2Me (R1 = R2 = H, H-Me, Me-Me, H-Ph) and H2NCH2CH2CO2Me in CH2Cl2 produces the amidine complexes trans-[PtCl4 Z-NH=C(Et)NHC(R1)(R2)CO2Me}2] and trans-[PtCl4 Z-NH=C(Et)NHCH2CH2CO2Me}2], which were isolated in 70–80% yields and characterized by elemental analysis, mass spectrometry, IR spectroscopy

  腈铂(IV)配合物反式-[PtCl4(EtCN)2]与氨基酸酯H2NC(R1)(R2)CO2Me的反应（R1 = R2 = H, H-Me, Me-Me, H-Ph）和 H2NCH2CH2CO2Me 在 CH2Cl2 中产生脒配合物反式-[PtCl4 Z-NH=C(Et)NHC(R1)(R2)CO2Me}2] 和反式-[PtCl4 Z-NH=C(Et)NHCH2CH2CO2Me}2] ，其以 70-80% 的产率分离，并通过元素分析、质谱、红外光谱以及 1H 和 13C1H} NMR 光谱表征。通过X射线衍射分析确定了R1 = R2 = H (1)、R1 = H、R2 = Me (2)和R1 = H、R2 = Ph (4)的配合物的结构。
• Pop-the-Cork Strategy in Synthetic Utilization of Imines:  Stabilization by Complexation and Activation via Liberation of the Ligated Species
  作者：Nadezhda A. Bokach、Vadim Yu. Kukushkin、Matti Haukka、João J. R. Fraústo da Silva、Armando J. L. Pombeiro

  DOI：10.1021/ic034086j

  日期：2003.6.1

  allowed the isolation of trans-[PtCl(4)[E-NH[double bond]C(R)OEt](2)]. The latter were reduced selectively, by the ylide Ph(3)P[double bond]CHCO(2)Me, to trans-[PtCl(2)[E-NH[double bond]C(R)OEt](2)]. The complexed imino esters NH[double bond]C(R)OEt were liberated from the platinum(II) complexes by reaction with 2 equiv of 1,2-bis(diphenylphosphino)ethane (dppe) in chloroform; the cationic complex [Pt(dppe)(2)]Cl(2)

  用乙醇处理反式-[PtCl（4）（RCN）（​​2）]（R = Me，Et）可分离反式-[PtCl（4）[E-NH [双键] C（R）OEt] （2）]。后者被叶立德Ph（3）P [双键] CHCO（2）Me选择性还原为反式-[PtCl（2）[E-NH [双键] C（R）OEt]（2）] 。通过与2当量的1，2-双（二苯基膦基）乙烷（dppe）在氯仿中反应，从铂（II）配合物中释放出络合的亚氨基酯NH [双键] C（R）OEt。阳离子络合物[Pt（dppe）（2）] Cl（2）几乎从反应混合物中沉淀出来，可以很容易地通过过滤分离，得到已知浓度的NH [双键] C（R）OEt溶液。亚氨基酯。亚氨基酯可与反式-[PtCl（4）（EtCN）（2）]中的配位腈有效偶联，从而得到占主导地位的产物 [PtCl（4）[NH [双键] C（Et）N [双键CC（R）OEt]（2）]包含先前未知的键合，即连