二氯化四(二甲基亚砜)合钌(II)

化合物

二氯化四(二甲基亚砜)合钌(II)是一种配位化合物,化学式为RuCl2(DMSO)4,其中,DMSO为二甲基亚砜的英文缩写。它存在顺式和反式两种构型,这两种构型都是已知的,但顺式构型(如右图)更为常见。顺式异构体为黄色固体,在空气中稳定,可溶于一部分有机溶剂。它是潜在的抗癌药物。

Dichlorotetrakis(dimethyl sulfoxide) ruthenium (II)
系统名
Ruthenium, dichlorotetrakis(sulfinylbis(methane))- (9CI)
别名 二氯四(二甲亚砜)合钌
四(二甲基亚砜)二氯化钌
氯化四(二甲基亚砜)合钌(II)
识别
CAS号 41290-68-0(S,S,S,O)  checkY
59091-96-2cis-S,S,S,O)  checkY
89395-66-4(S,S,S,S)  checkY
64376-67-6cis-S,S,S,S)  checkY
72904-47-3trans-S,S,S,S)  checkY
75766-08-4trans-S,S,S,O)  checkY
性质
化学式 C8H24Cl2O4RuS4
摩尔质量 484.51 g·mol−1 g·mol⁻¹
外观 黄色晶体
溶解性 易溶于水
溶解性 硝基甲烷二氯甲烷氯仿1
结构
配位几何 八面体配位
若非注明,所有数据均出自标准状态(25 ℃,100 kPa)下。

结构与制备

顺式异构体为DMSO配体连接异构。[1]三个DMSO配体为S-键合,另一个为O-键合,对于两个Cl来说是顺式构型。反式异构体也是黄色的,但四个DMSO配体都是S-键合的。顺式可以通过热反应得到,而反式由顺式通过紫外线照射得到。[2]

 
 
cis,fac-异构体
trans,mer-异构体

这些配合物最初由三氯化钌的DMSO溶液在氢气气氛中加热得到。[3]另一种不使用氢气的方法也得到了文献报道。[2][4]

反应

顺式RuCl2(DMSO)4乙酰丙酮碳酸氢钠乙醇中回流反应,经提纯后可以得到黄色的顺式二(乙酰丙酮)二(二甲基亚砜)合钌(II)(cis-Ru(DMSO)2(acac)2)。[5]它和苯胺在常温下甲醇-氯仿(2:1)中反应,配位原子为氧的DMSO配体被取代,得到浅黄色的cis,fac-[RuCl2(DMSO)3(NH2C6H5)];若在甲醇中回流反应,则配位原子为氧和硫的两个DMSO配体被取代,得到深黄色的trans,cis,cis-[RuCl2(DMSO)2(NH2C6H5)2]。[6]

潜在应用

RuCl2(DMSO)4最初于20世纪80年代早期被认定为抗癌药。[7]后期进一步的研究[8][9]使得其它含DMSO的钌化合物得到了开发,其中一些进行了早期的临床试验。[10]

参考文献

  1. ^ Enzo Alessio. Synthesis and reactivity of Ru-, Os-, Rh-, and Ir-halide-sulfoxide compounds. Chem. Rev. 2004, 104 (9): 4203–4242. doi:10.1021/cr0307291. 
  2. ^ 2.0 2.1 I. Bratsos; E. Alessio. Ruthenium(II) Chloro Complexes of dimethylsulfoxide. Inorganic Syntheses. 2010, 35: 148–152. doi:10.1002/9780470651568.ch8. 
  3. ^ B. R. James; E. Ochiai; G.I. Rempel. Ruthenium (II) halide dimethylsulphoxide complexes from hydrogenation reactions. Inorganic and Nuclear Chemistry Letters. 1971, 7 (8): 781–784. doi:10.1016/0020-1650(71)80091-0. 
  4. ^ Nagy, E. M.; Pettenuzzo, A. Ruthenium(II/III)-Based Compounds with Encouraging Antiproliferative Activity against Non-small-Cell Lung Cancer. Chemistry: A European Journal. 2012, 18: 14464–14472. doi:10.1002/chem.201202171. 
  5. ^ Adam Wu, David C Kennedy, Brian O Patrick, Brian R James. Ruthenium(II) acetylacetonato–sulfoxide complexes. Inorganic Chemistry Communications. 2003-08, 6 (8): 996–1000 [2021-08-25]. doi:10.1016/S1387-7003(03)00164-3. (原始内容存档于2020-02-07) (英语). 页面存档备份,存于互联网档案馆
  6. ^ Daniele M. Martins, Pedro I. S. Maia, Valdemiro P. Carvalho-Jr, Benedito S. Lima-Neto. Cooperative Effects of Aniline with DMSO in Ru II Complexes: Tuning the Reactivity for Ring-Opening Metathesis Polymerization: Cooperative Effects of Aniline with DMSO in Ru II Complexes: Tuning the Reactivity for Ring-Opening Metathesis Polymerization. European Journal of Inorganic Chemistry. 2019-11-10, 2019 (41): 4421–4426 [2021-08-25]. doi:10.1002/ejic.201900887 (英语). 
  7. ^ Sava, Gianni; Giraldi, Tullio; Mestroni, Giovanni; Zassinovich, Grazia. Antitumor effects of rhodium(I), iridium(I) and ruthenium(II) complexes in comparison with cis-dichlorodiammino platinum(II) in mice bearing Lewis lung carcinoma. Chemico-Biological Interactions. July 1983, 45 (1): 1–6. doi:10.1016/0009-2797(83)90037-6. 
  8. ^ Coluccia, Mauro; Sava, Gianni; Loseto, Francesco; Nassi, Anna; Boccarelli, Angela; Giordano, Domenico; Alessio, Enzo; Mestroni, Giovanni. Anti-leukaemic action of RuCl2(DMSO)4 isomers and prevention of brain involvement on P388 leukaemia and on subline. European Journal of Cancer. January 1993, 29 (13): 1873–1879. doi:10.1016/0959-8049(93)90541-M. 
  9. ^ Bratsos, I; Serli, B; Zangranko, E; Katsaros, N; Alessio, E. Replacement of chlorides with dicarboxylate ligands in anticancer active Ru(II)-DMSO compounds: A new strategy that might lead to improved activity. Inorg. Chem. 2007, 46 (3): 975–992. PMID 17257042. doi:10.1021/ic0613964. 
  10. ^ Enzo Alessio, Bentham Science Publisher; Giovanni Mestroni, Bentham Science Publisher; Alberta Bergamo, Bentham Science Publisher; Gianni Sava, Bentham Science Publisher. Ruthenium Antimetastatic Agents. Current Topics in Medicinal Chemistry. 1 November 2004, 4 (15): 1525–1535. doi:10.2174/1568026043387421.