二氯化四(二甲基亚砜)合钌(II)

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） ; 59091-96-2（cis-S,S,S,O） ; 89395-66-4（S,S,S,S） ; 64376-67-6（cis-S,S,S,S） ; 72904-47-3（trans-S,S,S,S） ; 75766-08-4（trans-S,S,S,O）
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（水）	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。

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。

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和乙酰丙酮、碳酸氢钠在乙醇中回流反应，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

^ 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.
^ ^2.0 ^2.1 I. Bratsos; E. Alessio. Ruthenium(II) Chloro Complexes of dimethylsulfoxide. Inorganic Syntheses. 2010, 35: 148–152. doi:10.1002/9780470651568.ch8.
^ 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.
^ 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.
^ 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）
^ 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）.
^ 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.
^ 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.
^ 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.
^ 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.

[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.

[Bratsos2-2] 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.

[James-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.

[Bratsos-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.

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