Specific Synthesis and Reaction of Hetero- and Homobridged Diruthenium Carbonyl Complexes Containing One or Two -Azolato Bridges
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- 作者：Kom-Bei Shiu ; Wei-Ming Lee ; Chen-Lan Wang ; Sue-Lein Wang ; Fen-Ling Liao ; Ju-Chun Wang ; Lin-Shu Liou ; Shie-Ming Peng ; Gene-Hsiang Lee ; and Michael Y. Chiang
- 刊名：Organometallics
- 出版年：1996
- 出版时间：June 25, 1996
- 年：1996
- 卷：15
- 期：13
- 页码：2979 - 2987
- 全文大小：621K
- 年卷期：v.15,no.13(June 25, 1996)
- ISSN：1520-6041
文摘
Diruthenium(I) carbonyl complexes with either hetero- orhomobridges,[Ru2(
-Pz)2(CO)4(HPz)2] (1),[Ru2(-Pz')(-O2CMe)(CO)4(HPz')2](2), and[Ru2(-Pz')2(CO)4(HPz')2](3), can beprepared specifically. These complexes reacted with eithernucleophiles or electrophiles toproduce selectively only one product. The terminal azole groups,pyrazole (HPz) or 3,5-dimethylpyrazole (HPz'), of 1-3 are easilyreplaced by the phosphine ligands to give[Ru2(-Pz)2(CO)4(PPh3)2](4),[Ru2(-Pz')(-O2CMe)(CO)4(PPh3)2](5),[Ru2(-Pz')2(CO)4(PPh3)2](6),and[Ru2(-Pz)2(CO)4(
1-dppm)2](7). The -acetato bridge is more fragile than the-azolatobridge, and only the former bridge of 5 can be replaced byPz- and SR- to afford[Ru2(-Pz')(-Pz)(CO)4(PPh3)2](8) and[Ru2(-Pz')(-SR)(CO)4(PPh3)2](R = Ph (9), tBu (10)).Heatingthe mixture of 3 with dppm in THF gave a product retainingall the -azolato bridges butlosing two carbonyls,[Ru2(-Pz')2(CO)2(1,2-dppm)2](11), whereas a similar reaction between1-3 and nitrogen-bidentate ligands gaveproducts retaining all four carbonyls but only one-azolato bridge,[Ru2(-L)(-CO)2(CO)2(1,2-(N-N))2]+(L = Pz, N-N = bpy ([12]+),phen([13]+); L = Pz', N-N = bpy([14]+), phen([15]+)). The electrophilicaddition of 4 with I2produced[Ru2(-Pz)2(-I)(CO)4(PPh3)2][I3](16). The X-ray structure of this productconfirmsthe cleavage of the Ru-Ru bond rather than the -azolato bridges.However, the -azolatoand -acetato bridges, as well as the terminal azole groups, of1-6 can be easily removed byan electrophilc reagent such asEt3O+BF4- inthe presence of MeCN to give[Ru2(CO)4(MeCN)6][BF4]2 and[Ru2(CO)4(MeCN)4(PPh3)2][BF4]2.
-Pz)2(CO)4(HPz)2] (1),[Ru2(-Pz')(-O2CMe)(CO)4(HPz')2](2), and[Ru2(-Pz')2(CO)4(HPz')2](3), can beprepared specifically. These complexes reacted with eithernucleophiles or electrophiles toproduce selectively only one product. The terminal azole groups,pyrazole (HPz) or 3,5-dimethylpyrazole (HPz'), of 1-3 are easilyreplaced by the phosphine ligands to give[Ru2(-Pz)2(CO)4(PPh3)2](4),[Ru2(-Pz')(-O2CMe)(CO)4(PPh3)2](5),[Ru2(-Pz')2(CO)4(PPh3)2](6),and[Ru2(-Pz)2(CO)4(1-dppm)2](7). The -acetato bridge is more fragile than the-azolatobridge, and only the former bridge of 5 can be replaced byPz- and SR- to afford[Ru2(-Pz')(-Pz)(CO)4(PPh3)2](8) and[Ru2(-Pz')(-SR)(CO)4(PPh3)2](R = Ph (9), tBu (10)).Heatingthe mixture of 3 with dppm in THF gave a product retainingall the -azolato bridges butlosing two carbonyls,[Ru2(-Pz')2(CO)2(1,2-dppm)2](11), whereas a similar reaction between1-3 and nitrogen-bidentate ligands gaveproducts retaining all four carbonyls but only one-azolato bridge,[Ru2(-L)(-CO)2(CO)2(1,2-(N-N))2]+(L = Pz, N-N = bpy ([12]+),phen([13]+); L = Pz', N-N = bpy([14]+), phen([15]+)). The electrophilicaddition of 4 with I2produced[Ru2(-Pz)2(-I)(CO)4(PPh3)2][I3](16). The X-ray structure of this productconfirmsthe cleavage of the Ru-Ru bond rather than the -azolato bridges.However, the -azolatoand -acetato bridges, as well as the terminal azole groups, of1-6 can be easily removed byan electrophilc reagent such asEt3O+BF4- inthe presence of MeCN to give[Ru2(CO)4(MeCN)6][BF4]2 and[Ru2(CO)4(MeCN)4(PPh3)2][BF4]2.