trans-[PtCl₂(NCNMe₂)₂] | 178403-33-3

• 分子结构分类: 有机化合物 - 有机氮化合物
• 英文名称: trans-[PtCl₂(NCNMe₂)₂]
• 英文别名: dimethylcyanamide;platinum(2+);dichloride
• CAS: 178403-33-3
• 化学式: C₆H₁₂Cl₂N₄Pt
• 分子量: 406.174
• InChiKey: QQYRGDWQUHGHJJ-UHFFFAOYSA-L

计算性质

• 辛醇/水分配系数(LogP)：
  -5.94
• 重原子数：
  13
• 可旋转键数：
  2
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.67
• 拓扑面积：
  54.1
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  trans-[PtCl₂(NCNMe₂)₂] 在 氨 作用下， 反应 12.5h， 生成 cis-[Pt(ammonia)2(NHC(NH2)NMe2)2]Cl2
  参考文献：
  名称：

  Guanidine platinum(II) complexes: synthesis, in vitro antitumor activity, and DNA interactions

  摘要：

  The novel guanidine compounds trans-[Pt(NH2Me)(2)(NH=C(NHMe)NR)(2)(Cl)(2) (R = NEt2 [7], NC5H10 [8]) (trans-7,8) were synthesized by the nucleophilic addition of methylamine to dialkylcyanamide ligands of the push-pull nitrile complexes trans-[PtCl2(RCN)(2)] (R=NEt2, NC5H10). In vitro cytotoxicity tests conducted for the entire series of the guanidine complexes, i.e. trans-7,8, the neutral cis- or trans-[PtCl2{NH=C(NH2)R)2} (cis-1-3 and trans-1-3) and the cationic cis- or trans-[Pt(NH3)(2){NH=C(NH2)R}(2)](Cl)(2) (cis-4-6 and trans-4-6) (R = NMe2 [1,4], NEt2 [2,5], NC5H10 [3,6]) in two human cancer cell lines, CH1 (ovarian carcinoma) and SW480 (colon cancer), confirmed that the cytotoxicity of several trans-configured (trans-3,6) complexes is higher than that of cis-congeners (cis-3,6). Cellular platinum levels were analyzed by inductively coupled plasma mass spectrometry upon treatment of SW480 cells, revealing a dependence of cellular accumulation on the geometrical isomerism and the steric hindrance of the variable substituent R on the guanidine ligand. DNA interactions of selected guanidine complexes were studied in order to find hints for the possible reasons for their different activities. Changes induced to the electrophoretic mobility of a dsDNA plasmid confirmed the potency of the guanidine complexes (e.g. trans-1,3,5,6 and cis-1,3,4) to significantly alter DNA secondary structure, indicating DNA as a possible critical target of these compounds. (C) 2013 The Authors. Published by Elsevier Inc. All rights reserved.

  DOI：

  10.1016/j.jinorgbio.2013.12.007
• 作为产物：
  描述：

  trans-[PtCl2(2-NMe2-3a-Me-5,5,6,6-tetramethyl-3a,4,5,6-tetrahydroimidazo[1,2-b][1,2,4]oxadiazole)2]*0.25CH2Cl2 在 acetic acid 作用下， 以 氘代氯仿 为溶剂， 生成 trans-[PtCl₂(NCNMe₂)₂]
  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

• Hydrolytic Metal-Mediated Coupling of Dialkylcyanamides at a Pt(IV) Center Giving a New Family of Diimino Ligands
  作者：Nadezhda A. Bokach、Tatyana B. Pakhomova、Vadim Yu. Kukushkin、Matti Haukka、Armando J. L. Pombeiro

  DOI：10.1021/ic034800x

  日期：2003.11.1

  crystallography. Chlorination of the platinum(II) complexes cis-1-3 and trans-1-4 gives the appropriate platinum(IV) complexes [PtCl(4)(NCNR(2))(2)] (cis-5-7 and trans-5-8). The compound cis-6 was also obtained by treatment of [PtCl(4)(NCMe)(2)] with neat Et(2)NCN. The platinum(IV) complex trans-[PtCl(4)(NCNMe(2))(2)] (trans-5) in a mixture of undried Et(2)O and CH(2)Cl(2) undergoes facile hydrolysis to

  向K（2）[PtCl（4）]的水溶液中添加过量的R（2）NCN导致[PtCl（2）（NCNR（2））（2）]沉淀（R（2）= Me （2）1； Et（2）2； C（5）H（10）3； C（4）H（8）O，4）的顺/反异构体比例取决于温度。通过SiO（2）上的柱色谱分离纯净的异构体顺式1-3和反式1-3，而通过重结晶获得反式-4。固相加热至110摄氏度时，配合物顺式1-3异构化为反式1-3。通过X射线晶体学对trans-1进行了表征。氯化铂（II）配合物顺式1-3和反式1-4得到适当的铂（IV）配合物[PtCl（4）（NCNR（2））（2）]（顺式5-7和反式-5-8）。通过用纯Et（2）NCN处理[PtCl（4）（NCMe）（2）]，也可以获得化合物cis-6。在未干燥的Et（2）O和CH（2）Cl（2）的混合物中的铂（IV）络合物反式[[PtCl（4）（NCNMe（2））（2）]（tra
• 2-Amino-2-oxazoline and trialkylisourea Pt(<scp>ii</scp>) complexes derived from organocyanamides
  作者：Cristina M. P. Ferreira、M. Fátima C. Guedes da Silva、Rino A. Michelin、Vadim Yu. Kukushkin、João J. R. Fraústo da Silva、Armando J. L. Pombeiro

  DOI：10.1039/b306690h

  日期：——

  In the di(organocyanamide) complexes trans-[PtCl2(NCNR2)2] (R = Me 1a, Et 1b), prepared by reaction of PtCl2 with the appropriate NCNR2, the cyanamide ligands, activated by coordination, undergo an unprecedented nucleophilic addition, at room temperature, of an haloalcohol (ClCH2CH2OH/LiBun) or of an alcohol (MeOH) to give the corresponding 2-amino-2-oxazoline cis-[PtCl2NC(OCH2CH2)NR2}2] (R = Me 2a, Et 2b) or trialkylisourea trans-[PtCl2NHC(OMe)NR2}2] (R = Me 3a, Et 3b) complexes. The X-ray crystal structure of 2b is also reported, indicating a π-bond delocalization along the NCN group of the aminooxazoline ligands.

  在由 PtCl2 与适当的 NCNR2 反应制备的反式-[PtCl2(NCNR2)2]（R = Me 1a，Et 1b）二（有机氰酰胺）配合物中，通过配位活化的氰酰胺配体发生了前所未有的亲核加成反应、在室温下，与卤代醇（ClCH2CH2OH/LiBun）或醇（MeOH）发生前所未有的亲核加成反应，得到相应的 2-氨基-2-噁唑啉顺式-[PtCl2NC(OCH2CH2)NR2}2]（R = Me 2a，Et 2b）或三烷基异脲反式-[PtCl2NHC(OMe)NR2}2]（R = Me 3a，Et 3b）配合物。此外，还报告了 2b 的 X 射线晶体结构，表明沿着氨基噁唑啉配体的 NCN 基团存在 π 键外焦作用。
• Facile cyanamide–ammonia coupling mediated by cis- and trans-[PtIIL2] centers and giving metal-bound guanidines
  作者：Marina R. Tyan、Nadezhda A. Bokach、Meng-Jiy Wang、Matti Haukka、Maxim L. Kuznetsov、Vadim Yu. Kukushkin

  DOI：10.1039/b806862c

  日期：——

  cis- or trans-[PtCl(2)(RCN)(2)] (R = NMe(2), NEt(2), NC(5)H(10)) at 20-25 degrees C leads to metal-mediated cyanamide-ammonia coupling to furnish, depending on reaction time, one or another type of novel bisguanidine compound, i.e. the molecular cis- or trans-[PtCl(2)NH=C(NH(2))R}(2)] (cis- and trans-) and the cationic cis- or trans-[Pt(NH(3))(2)NH=C(NH(2))R}(2)](Cl)(2) (cis- and trans-) complexes

  氨扩散到二烷基氰酰胺配合物顺式或反式[PtCl（2）（RCN）（​​2）]的CH（2）Cl（2）解决方案中（R = NMe（2），NEt（2），NC（5） ）H（10））在20-25摄氏度下导致金属介导的氰酰胺-氨偶合，从而根据反应时间而提供一种或另一种新型双胍化合物，即分子顺式或反式[PtCl（2） ）NH = C（NH（2））R}（2）]（顺式和反式）和阳离子顺式或反式-[Pt（NH（3））（2）NH = C（NH（ 2））R}（2）]（Cl）（2）（顺式和反式）配合物。因此，在NH（3）在CH（2）Cl（2）中长时间处理后，化合物顺式或反式被转换为顺式或反式。在CH（2）Cl（2）解决方案中相关腈配合物的顺式或反式[PtCl（2）（RCN）（​​2）]（R = Et，CH（2）Ph，Ph）的氨化仅提供阳离子化合物顺式或反式-[Pt（NH（3））（2）NH = C（NH（2））R
• Dialkylcyanamides are more reactive substrates toward metal-mediated nucleophilic addition than alkylcyanides
  作者：Tatyana B. Anisimova、Nadezhda A. Bokach、Fedor M. Dolgushin、Vadim Yu. Kukushkin

  DOI：10.1039/c3dt51137e

  日期：——

  (Q = Ph3PCH2Ph, R2 = Me21, Et22, C5H103, C4H8O 4; Q = NMe4, R2 = Me25; Q = NEt4, R2 = Me26) were synthesized either by dissolving Q2[Pt2(mu-Cl)2Cl4] in neat NCNR2 (1-4) or by substitution of a NCNR2 ligand with Cl(-) in [PtCl2(NCNR2)2] by its treatment with QCl (5, 6). Nucleophilic addition of dibenzylhydroxylamine, HON(CH2Ph)2, to 1-6 results in the formation of the complexes Q[PtCl3NHC(NR2)ON(CH2Ph)2}]

  通过溶解Q2 [Pt2]合成了二烷基氰酰胺配合物Q [PtCl3（NCNR2）]（Q = Ph3PCH2Ph，R2 = Me21，Et22， 3，C4H8O 4; Q = NMe4，R2 = Me25; Q = NEt4，R2 = Me26）。 （mu-Cl）2Cl4]在纯净的NCNR2（1-4）中，或用[PtCl2（NCNR2）2]中的Cl（-）取代NCNR2配体，用QCl处理（5，6）。向1-6亲核添加二苄基羟胺HON（CH2Ph）2导致形成配合物Q [PtCl3 NHC（NR2）ON（CH2Ph）2}]（Q = Ph3PCH2Ph，R2 = Me2，7; Et2， 8; C5H10，9; ，10; Q = Me4N，R2 = Me211; Q = Et4N，R2 = Me2，12）在室温下以固态（1-24 h）或在溶液中（0.5）进一步转化-2 h）形成亚胺配合物Q
• Highly Stereoselective 1,3-Dipolar Cycloaddition of Nitrones to (Nitrile)₂Pt^II Species Furnishing Diastereomerically Pure 2,3-Dihydro-1,2,4-oxadiazole Ligands
  作者：Nadezhda A. Bokach、Irina A. Balova、Matti Haukka、Vadim Yu. Kukushkin

  DOI：10.1021/om100957b

  日期：2011.2.14

  Diastereomerically pure platinum(II) complexes 4−9 bearing tetrahydro-5,8-methanocyclohexa[3′,2′:4,5][1,3]oxazolo[3,2-b][1,2,4]oxadiazole ligands were generated under mild conditions (CH2Cl2, 20−25 °C, 24 h) by an intermolecular PtII-mediated 1,3-dipolar cycloaddition between enantiomerically pure camphor-derived oxazoline-N-oxides and the coordinated nitriles in the complexes trans-[PtCl2(R′CN)2] (R′ = Et, Ph, NMe2)

  对映异构纯铂（II）络合物4 - 9轴承四氢-5,8- methanocyclohexa [3'，2'：4,5] [1,3]恶唑并[3,2- b ] [1,2,4]恶二唑温和的条件下产生的配体（CH 2氯2，20-25℃，24小时）通过分子间的Pt II介导之间对映体纯樟脑衍生oxazoline- 1,3-偶极环加成ñ -oxides和协调在腈该复合物反式为[PtCl 2（R'CN）2 ]（R'= Et，Ph，NMe 2）。这些物种的特征在于元素分析（C，H，N），高分辨率ESI + -MS，IR，1H和13个C NMR波谱，并且还X射线衍射（对于5，7，8 ·氯仿3，和9 ·我2 CO）。自由杂环10 - 13被解放从（2,3-二氢-1,2,4-恶二唑）单一立体异构体2的Pt II复合物（R =的Et，PH）通过用过量的NaCN处理和表征由高分辨率ESI + -MS和1 H和13 C NMR光谱。