di‑μ‑chloro‑bis(N,N‑dimethylbenzylamine‑2‑C,N)diplatinum(II) | 18987-58-1

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: di‑μ‑chloro‑bis(N,N‑dimethylbenzylamine‑2‑C,N)diplatinum(II)
• 英文别名: [Pt₂(dmba)₂Cl₂]；[Pt(dmba)Cl]₂；[Pt(μ-Cl)(N,N-dimethylbenzylamine)]2；chloroplatinum(1+);N,N-dimethyl-1-phenylmethanamine
• CAS: 18987-58-1
• 化学式: C₁₈H₂₄Cl₂N₂Pt₂
• 分子量: 729.468
• InChiKey: HQSFARLBBJBOTR-UHFFFAOYSA-L

计算性质

• 辛醇/水分配系数(LogP)：
  4.47
• 重原子数：
  24
• 可旋转键数：
  4
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.33
• 拓扑面积：
  6.5
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  tricarbonyl(η⁶-2-methylindenyl)chromium(0) 、 di‑μ‑chloro‑bis(N,N‑dimethylbenzylamine‑2‑C,N)diplatinum(II) 在 正丁基锂 作用下， 以 氯仿 为溶剂， 反应 17.0h， 以12%的产率得到cis-[tricarbonyl(η⁶-2-methylindenyl)-chromium(0),κC¹,κ{Cr(CO)₃}](N,N-dimethyl,phenylene,-methylamine,κC¹,κN)platinum(II)
  参考文献：
  名称：

  半螯合，一种稳定电子不饱和配合物的方法：T 形 Pd 和 Pt 金属环的情况。

  摘要：

  提出了一种合成稳定的中性T形14电子Pd和Pt配合物的合理方法。它利用了三羰基(η(6)-茚基)铬阴离子的两亲性，其主要特性是作为半螯合配体，即一种非常规的异双位配体，能够通过共价键螯合金属中心。和非共价键，从而保持其不饱和价壳。原位形成的三羰基（η(6)-2-甲基茚基）铬阴离子与一系列 Pd 和 Pt 金属环的反应提供了新的空气稳定和持久的异质双金属配合物，其中金属环通过其金属结合茚基片段η(1) 方式，使螯合金属处的第四配位位点几乎空置。公开了这些新型复合物中的八种结构，并通过基于密度泛函理论的一系列理论方法（NBO、EDA、ETS-NOCV、AIM、NCI 区域分析）研究了它们的键合特征。理论表明，这些不寻常的双金属共面 η(1)-茚基-Pd/Pt 复合物结构的形成是由 Cr(CO)3 部分在 Pd/Pt 中心的第四个空位配位位点的吸引力库仑闭塞热力学驱动的。

  DOI：

  10.1021/ja4076327
• 作为产物：
  描述：

  苯甲醛 在 titanium(IV) isopropylate 、 三乙胺 作用下， 以 甲醇 、 乙醇 、 水 为溶剂， 反应 42.0h， 生成 di‑μ‑chloro‑bis(N,N‑dimethylbenzylamine‑2‑C,N)diplatinum(II)
  参考文献：
  名称：

  Dual Antitumor and Antiangiogenic Activity of Organoplatinum(II) Complexes

  摘要：

  A library of over 20 cycloplatinated compounds of the type [Pt(dmba-R)LCl] (dmba-R = C,N-dimethylbenzylamine-like ligand; R being MeO, Me, H, Br, F, CF3, and NO2 substituents in the R-5 or R-4 position of the phenyl ring; L = DMSO and P(C6H4CF3-p)(3)) has been prepared. All compounds are active in both human ovarian carcinoma A2780 cells and cisplatin-resistant A2780cisR cells, with most of the DMSO platinum complexes exhibiting IC50 values in the submicromolar range in the A2780 cell line. Interestingly, DMSO platinum complexes show low cytotoxicity in the nontumorigenic kidney cell line BGM and therefore high selectivity factors SF. In addition, some of the DMSO platinum complexes effectively inhibit angiogenesis in the human umbilical vein endothelial cell line EA.hy926. These are the first platinum(II) complexes reported to inhibit angiogenesis at a close concentration to their IC50 in A2780 cells, turning them into dual cytotoxic and antiangiogenic compounds.

  DOI：

  10.1021/jm501662b

文献信息

• Pseudo-rotation mechanism for fast olefin exchange and substitution processes at orthometalated C,N-complexes of platinum(ii)
  作者：Stefanus Otto、Pavel V. Samuleev、Vladimir A. Polyakov、Alexander D. Ryabov、Lars I. Elding

  DOI：10.1039/b409887k

  日期：——

  allyl alcohol and phosphine according to 1+ 2L --> 2[PtCl(2-Me(2)NCH(2)C(6)H(4))(L)], where L = C(2)H(4)(3a), C(8)H(14), (3b), CH(2)CHCH(2)OH (3c), and PPh(3)(4a and 4b) gives monomeric species with L coordinated trans or cis to aryl. With olefins the thermodynamically stable isomer with L coordinated cis to aryl is formed directly without an observable intermediate. With phosphine and pyridine, the

  氯仿的正金属化氯桥联络合物[Pt（micro-Cl）（2-Me（2）NCH（2）C（6）H（4））]（2）（1）的氯仿中的乙烯，环辛烯，烯丙醇和膦根据1+ 2L-> 2 [PtCl（2-Me（2）NCH（2）C（6）H（4））（L）]，其中L = C（2）H（ 4）（3a），C（8）H（14），（3b），CH（2）CHCH（2）OH（3c）和PPh（3）（4a和4b）给出具有L配位反式或顺式为芳基。对于烯烃，直接形成L配位为芳基的热力学稳定的异构体，而没有可观察到的中间体。用膦和吡啶，动力学控制的反式产物缓慢异构化为更稳定的顺式异构体。用烯烃进行的桥裂很慢，并且在1和L中都是一阶的，DeltaS（++）在很大程度上是负数。环辛烯和烯丙醇将乙烯顺式取代为芳基，形成3b和3c，在烯烃和络合物中，由烯丙基醇将3b取代成3c形成3c是一阶的。由于DeltaH（++）的大幅降低，并且DeltaS（+
• Functionalized azobenzene platinum(II) complexes as putative anticancer compounds
  作者：Katia G. Samper、Julia Lorenzo、Mercè Capdevila、Òscar Palacios、Pau Bayón

  DOI：10.1007/s00775-021-01865-9

  日期：2021.6

  mechanism of action of these complexes as cytostatic agents. The interaction of the compounds with DNA, studied by circular dichroism, revealed a differential activity of the Pt(II) complexes upon irradiation. The intercalation abilities of the complexes as well as their reactivity with common proteins present in the blood stream allows to confirm some of the compounds obtained as good anticancer candidates

  已经进行了使用方便地功能化的偶氮苯作为配体的四种铂 (II) 配合物的合成和表征。由于偶氮苯型配体的存在以及配体在配合物活化中的作用，研究了配合物的特征光化学行为。它们在 HeLa 细胞中观察到的有希望的细胞毒性促使我们研究这些复合物作为细胞抑制剂的作用机制。通过圆二色性研究化合物与 DNA 的相互作用揭示了 Pt(II) 复合物在辐照时的不同活性。复合物的嵌入能力以及它们与血流中常见蛋白质的反应性允许确认获得的一些化合物是良好的抗癌候选物。
• Amine-functionalised aminophosphines: synthesis, reversible co-ordination to platinum and use in heteronuclear dimer formation
  作者：Andrew D. Burrows、Mary F. Mahon、Mark T. Palmer

  DOI：10.1039/b005899h

  日期：——

  Amine functionalised aminophosphines Ph2PN(R)CH2CH2NMe2 (R = H L1 or Me L2) were prepared from the reaction of PPh2Cl with NHRCH2CH2NMe2 in the presence of the base n-butyllithium (L1) or triethylamine (L2). Reaction of two equivalents of L1,2 with [PtCl2(cod)] gave the complexes cis-[PtCl2L2] (L = L11 or L22), which were shown to be fluxional with one of the amine groups reversibly co-ordinating to displace a chloride. Removal of a chloride in 1 by metathesis gave cis-[PtCl(L1-P)(L1-P,N)]PF63 which was not fluxional on the NMR timescale. Reaction of one equivalent of L2 with [PtCl2(cod)] gave the complex cis-[PtCl2(L2-P,N)] 4 in which L2 is acting as a bidentate ligand. The reaction of L2 with [Pt(dmba)(μ-Cl)}2] (Hdmba = N,N-dimethylbenzylamine) gave [Pt(dmba)Cl(L2)] 5, which exists as a mixture of the two geometric isomers. Reaction of 5 with TlPF6 gave [Pt(dmba)(L2-P,N)]-PF66 as a single isomer in which the phosphorus atom is co-ordinated trans to the N,N-dimethylbenzylamine nitrogen atom. Complex 2 reacts with CoCl2·6H2O and ZnCl2 to give cis-[(L2-P,N)ClPt(μ-L2)MCl3] (M = Co 7 or Zn 8). The zwitterionic structure of 7 was confirmed by a single-crystal X-ray analysis, which showed no metal–metal interaction between the platinum and cobalt centres.

  胺官能化氨基膦 Ph2PN(R)CH2CH2NMe2（R = H L1 或 Me L2）由 PPh2Cl 与 NHRCH2CH2NMe2 在碱正丁基锂 (L1) 或三乙胺 (L2) 存在下反应制备。两当量的 L1,2 与 [PtCl2(cod)] 反应，得到配合物 cis-[PtCl2L2]（L = L11 或 L22），该配合物被证明与其中一个胺基团可逆地配位以取代一个胺基团。氯化物。通过复分解除去1中的氯化物得到顺式-[PtCl(L1-P)(L1-P,N)]PF63，其在NMR时间尺度上不流动。一当量的 L2 与 [PtCl2(cod)] 反应得到配合物 cis-[PtCl2(L2-P,N)] 4，其中 L2 充当二齿配体。 L2 与 [Pt(dmba)(μ-Cl)}2] (Hdmba = N,N-二甲基苄胺) 反应得到 [Pt(dmba)Cl(L2)] 5，它作为两种几何形状的混合物存在异构体。 5与TlPF6反应得到单一异构体[Pt(dmba)(L2-P,N)]-PF66，其中磷原子与N,N-二甲基苄胺氮原子反式配位。配合物 2 与 CoCl2·6H2O 和 ZnCl2 反应生成顺式-[(L2-P,N)ClPt(μ-L2)MCl3]（M = Co 7 或 Zn 8）。单晶X射线分析证实了7的两性离子结构，表明铂和钴中心之间没有金属-金属相互作用。
• Anticancer C,N-Cycloplatinated(II) Complexes Containing Fluorinated Phosphine Ligands: Synthesis, Structural Characterization, and Biological Activity
  作者：Natalia Cutillas、Alexandra Martínez、Gorakh S. Yellol、Venancio Rodríguez、Ana Zamora、Mónica Pedreño、Antonio Donaire、Christoph Janiak、José Ruiz

  DOI：10.1021/ic401973k

  日期：2013.12.2

  A series of potent C,N-cycloplatinated(II) phosphine antitumor complexes containing fluorous substituents in the cyclometalated or the ancillary phosphine ligands [Pt(C-N)(PR3)Cl] or both have been synthesized and characterized. The crystal structure of [Pt(dmba)P-(C6H4CF3-p)(3)}Cl]center dot 2CH(2)Cl(2) (dmba = dimethylaminomethyl)phenyl) has been established by X-ray diffraction. Values of IC50 of the new platinum complexes were calculated toward a panel of human tumor cell lines representative of ovarian (A2780 and A2780cisR) and breast cancers (T47D). Complexes containing P(C6H4CF3-p)(3) as ancillary ligand (with a bulky and electronegative CF3 substituent in para position) were the most cytotoxic compounds in all the tested cancer cell lines. In some cases, the IC50 values were 16-fold smaller than that of cisplatin and 11-fold smaller than the non-fluorous analogue [Pt(dmba)(PPh3)Cl]. On the other hand, very low resistance factors (RF) in A2780cisR (cisplatin-resistant ovarian carcinoma) at 48 h were observed (RF approximate to 1) for most of the new compounds. Analysis of cell cycle was done for the three more active compounds in A2780. They arrest cell growth in G0/G1 phase in contrast to cisplatin (S phase) with a high incidence of late-stage apoptosis. They are also good cathepsin B inhibitors (an enzyme implicated in a number of cancer related events).
• Targeting of Pallada- and Platinacycles to the <i>N</i>-((<i>tert</i>-Butyloxy)carbonyl)-<scp>l</scp>-methionine <i>p</i>-Nitrophenyl Ester for Promotion of the Ester Cleavage
  作者：Elena V. Krooglyak、Gregory M. Kazankov、Sergei A. Kurzeev、Vladimir A. Polyakov、Anatole N. Semenov、Alexander D. Ryabov

  DOI：10.1021/ic951180u

  日期：1996.1.1