二氯化四(二甲基亞碸)合釕(II)

Dichlorotetrakis(dimethyl sulfoxide) ruthenium (II)
	系統名; Ruthenium, dichlorotetrakis(sulfinylbis(methane))- (9CI)
別名	二氯四(二甲亞碸)合釕; 四(二甲基亞碸)二氯化釕; 氯化四(二甲基亞碸)合釕(II)
識別
CAS號	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）
性質
化學式	C8H24Cl2O4RuS4
摩爾質量	484.51 g·mol−1 g·mol⁻¹
外觀	黃色晶體
溶解性（水）	易溶於水
溶解性	硝基甲烷、二氯甲烷、氯仿1
結構
配位幾何	八面體配位
	若非註明，所有數據均出自標準狀態（25 ℃，100 kPa）下。

二氯化四(二甲基亞碸)合釕(II)是一種配位化合物，化學式為RuCl₂(DMSO)₄，其中，DMSO為二甲基亞碸的英文縮寫。它存在順式和反式兩種構型，這兩種構型都是已知的，但順式構型（如右圖）更為常見。順式異構體為黃色固體，在空氣中穩定，可溶於一部分有機溶劑。它是潛在的抗癌藥物。

結構與製備[編輯]

順式異構體為DMSO配體連接異構。^[1]三個DMSO配體為S-鍵合，另一個為O-鍵合，對於兩個Cl來說是順式構型。反式異構體也是黃色的，但四個DMSO配體都是S-鍵合的。順式可以通過熱反應得到，而反式由順式通過紫外線照射得到。^[2]


cis,fac-異構體	trans,mer-異構體

這些配合物最初由三氯化釕的DMSO溶液在氫氣氣氛中加熱得到。^[3]另一種不使用氫氣的方法也得到了文獻報道。^[2]^[4]

反應[編輯]

順式RuCl₂(DMSO)₄和乙酰丙酮、碳酸氫鈉在乙醇中回流反應，經提純後可以得到黃色的順式二(乙酰丙酮)二(二甲基亞碸)合釕(II)（cis-Ru(DMSO)₂(acac)₂）。^[5]它和苯胺在常溫下甲醇-氯仿（2:1）中反應，配位原子為氧的DMSO配體被取代，得到淺黃色的cis,fac-[RuCl₂(DMSO)₃(NH₂C₆H₅)]；若在甲醇中回流反應，則配位原子為氧和硫的兩個DMSO配體被取代，得到深黃色的trans,cis,cis-[RuCl₂(DMSO)₂(NH₂C₆H₅)₂]。^[6]

潛在應用[編輯]

RuCl₂(DMSO)₄最初於20世紀80年代早期被認定為抗癌藥。^[7]後期進一步的研究^[8]^[9]使得其它含DMSO的釕化合物得到了開發，其中一些進行了早期的臨床試驗。^[10]

參考文獻[編輯]

^ 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. （原始內容存檔於2020-02-07）（英語）. （頁面存檔備份，存於網際網路檔案館）
^ 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 （英語）.
^ 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. （原始內容存檔於2020-02-07）（英語）. （頁面存檔備份，存於網際網路檔案館）

[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 （英語）.

[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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