Synthesis, Structures, Solution Behavior, and Reactions of Thiolato-Bridged Diruthenium Carbonyl Phosphine Complexes
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- 作者：Kom-Bei Shiu ; Sue-Lein Wang ; Fen-Ling Liao ; Michael Y. Chiang ; Shie-Ming Peng ; Gene-Hsiang Lee ; Ju-Chun Wang ; and Lin-Shu Liou
- 刊名：Organometallics
- 出版年：1998
- 出版时间：April 27, 1998
- 年：1998
- 卷：17
- 期：9
- 页码：1790 - 1797
- 全文大小：138K
- 年卷期：v.17,no.9(April 27, 1998)
- ISSN：1520-6041
文摘
Dinuclear thiolato-bridged complexes[Ru2(CO)4(
-SR)2(PR'3)2](R' = Ph, Me) have beenreadily prepared from the reaction of[Ru2(CO)4(MeCN)4(PR'3)2][BF4]2(R' = Ph (1), Me (2))with RSH (R = tBu,iPr, Ph) and Et3N at ambienttemperature. Although only the syn formof[Ru2(CO)4(-StBu)2(PPh3)2](3) and only the anti form of[Ru2(CO)4(-SPh)2(PMe3)2](6)were found, an equilibrium mixture of both the syn (isomerA) and anti (isomer B) formswas present in solution for[Ru2(CO)4(-SiPr)2(PPh3)2](4) and[Ru2(CO)4(-SPh)2(PPh3)2](5).The spectral data support that the syn form (4A) is themajor isomer of 4, while the antiform (5B) is the major isomer of 5. The twothiolato bridges are located cis to the twophosphine ligands in solid-state structures 3,4A, and 5B, but they are located cis toonlyone of the two ligands whereas they are trans to the other in structure6. Iodination of3-6gave one identical product[Ru2(CO)4(-SR)2I2(PR'3)2](R' = Ph, R = tBu (7),iPr (8), Ph(9);R' = Me, R = Ph (10)). Both spectral and structuralevidence shows that 7-10 exist inthesyn form with no Ru-Ru bonding interaction. The relativeorientation of the two thiolatobridges with respect to the two phosphine ligands present in6 remains in structure 10, inspite of the change from anti to syn. The reactions of thediiodide complexes[Ru2(CO)4(-SR)2I2(PR'3)2]with R''S anions give either[Ru2(CO)4(-SR)2(PR'3)2]and R''SSR'' or [Ru2(CO)4(-SR)2(SR'')2(PR'3)2].
-SR)2(PR'3)2](R' = Ph, Me) have beenreadily prepared from the reaction of[Ru2(CO)4(MeCN)4(PR'3)2][BF4]2(R' = Ph (1), Me (2))with RSH (R = tBu,iPr, Ph) and Et3N at ambienttemperature. Although only the syn formof[Ru2(CO)4(-StBu)2(PPh3)2](3) and only the anti form of[Ru2(CO)4(-SPh)2(PMe3)2](6)were found, an equilibrium mixture of both the syn (isomerA) and anti (isomer B) formswas present in solution for[Ru2(CO)4(-SiPr)2(PPh3)2](4) and[Ru2(CO)4(-SPh)2(PPh3)2](5).The spectral data support that the syn form (4A) is themajor isomer of 4, while the antiform (5B) is the major isomer of 5. The twothiolato bridges are located cis to the twophosphine ligands in solid-state structures 3,4A, and 5B, but they are located cis toonlyone of the two ligands whereas they are trans to the other in structure6. Iodination of3-6gave one identical product[Ru2(CO)4(-SR)2I2(PR'3)2](R' = Ph, R = tBu (7),iPr (8), Ph(9);R' = Me, R = Ph (10)). Both spectral and structuralevidence shows that 7-10 exist inthesyn form with no Ru-Ru bonding interaction. The relativeorientation of the two thiolatobridges with respect to the two phosphine ligands present in6 remains in structure 10, inspite of the change from anti to syn. The reactions of thediiodide complexes[Ru2(CO)4(-SR)2I2(PR'3)2]with R''S anions give either[Ru2(CO)4(-SR)2(PR'3)2]and R''SSR'' or [Ru2(CO)4(-SR)2(SR'')2(PR'3)2].