177562-41-3

Upstream product

• 366-18-7 [2,2]bipyridinyl 
• 177562-49-1 Ru₂(CO)4(C₃H₃N₂)2(C₃H₄N₂)2 
• 143-66-8 sodium tetraphenyl borate 

Relevant academic research and scientific papers

Specific synthesis and reaction of hetero- and homobridged diruthenium carbonyl complexes containing one or two μ-azolato bridges

Diruthenium(I) carbonyl complexes with either hetero- or homobridges, [Ru2(μ-Pz)2(CO)4-(HPz)2] (1), [Ru2(μ-Pz′)(μ-O2CMe)(CO) 4(HPz′)2] (2), and [Ru2(μ-Pz′)2(CO)4(HPz′)2] (3), can be prepared specifically. These complexes reacted with either nucleophiles or electrophiles to produce selectively only one product. The terminal azole groups, pyrazole (HPz) or 3,5-dimethylpyrazole (HPz′), of 1-3 are easily replaced by the phosphine ligands to give [Ru2-(μ-Pz)2(CO)4(PPh3) 2] (4), [Ru2(μ-Pz′)(μ-O2CMe)(CO)4(PPh 3)2] (5), [Ru2(μ-Pz′)2(CO)4(PPh 3)2] (6), and [Ru2(μ-Pz)2(CO)4(η 1-dppm)2] (7). The μ-acetato bridge is more fragile than the μ-azolato bridge, and only the former bridge of 5 can be replaced by Pz- and SR- to afford [Ru2(μ-Pz′)(μ-Pz)(CO)4(PPh3) 2] (8) and [Ru2(μ-Pz′)(μ-SR)(CO)4(PPh3) 2] (R = Ph (9), tBu (10)). Heating the mixture of 3 with dppm in THF gave a product retaining all the μ-azolato bridges but losing two carbonyls, [Ru2(M-Pz′)2(CO)2(μ 1,η2-dppm)2] (11), whereas a similar reaction between 1-3 and nitrogen-bidentate ligands gave products retaining all four carbonyls but only one μ-azolato bridge, [Ru2(μ-L)(μ-CO)2(CO)2(μ 1,η2-(N-N))2]+ (L = Pz, N-N = bpy ([12]+), phen ([13]+); L = Pz′, N-N = bpy ([14]+), phen ([15]+)). The electrophilic addition of 4 with I2 produced [Ru2(μ-Pz)2(μ-I)(CO)4(PPh 3)2][I3] (16). The X-ray structure of this product confirms the cleavage of the Ru-Ru bond rather than the μ-azolato bridges. However, the μ-azolato and -acetato bridges, as well as the terminal azole groups, of 1-6 can be easily removed by an electrophilc reagent such as Et3O+BF4- in the presence of MeCN to give [Ru2(CO)4-(MeCN)6][BF4]2 and [Ru2(CO)4(MeCN)4(PPh3) 2][BF4]2.