Versatile and highly efficient synthesis of diruthenium tetrahydride complex

Selective Synthesis of a Triruthenium Pentahydrido Complex with Mixed-Cp Ligands (C5tBu3H2 and C5Me5) and Its Transformation into Face-Capping Benzene Complexes: Fluxionality of a Face-Capping Benzene Ligand Induced by Oxidation

“…In fact, the subsequent treatment of 7 with 2-propanol in the presence of KOH resulted in the clean formation of 1b . Notably, formation of 7 was necessary prior to the additions of 2-propanol and KOH to avoid the formation of [{Cp ‡ Ru­(μ-H) 2 } 2 ] ( 5b ), which is formed under similar conditions . Complex 1b was isolated in 43% yield by recrystallization, based on the use of 5a .…”

Syntheses and Properties of Triruthenium Polyhydrido Complexes Composed of 1,2,4-tri-tert-butylcyclopentadienyl and p-Cymene Ruthenium Units

“…The nuclearity of a polyhydrido cluster is highly influenced by the bulkiness of the supporting ligand; while only diruthenium complex 1b was obtained from [Cp ‡ RuCl 2 ] 2 , as mentioned in the Introduction, a triruthenium pentahydrido complex, [{Cp*Ru­(μ-H)} 3 (μ 3 -H) 2 ] ( 6 ), was obtained in 96% yield by the reaction of the less sterically demanding [Cp*RuCl 2 ] 2 complex (eq ). Ohki et al demonstrated that a hydrido-bridged dinuclear complex was exclusively obtained using a bulky Cp ‡ ligand …”

“…C 6 D 6 and THF-d 8 were dried over sodium-benzophenone ketyl and stored under an atmosphere of argon. [Cp*RuCl 2 ] 2 , 54 [Cp ‡ RuCl] 2 , 55 and [(Cp ‡ Ru) 2 (μ-H) 4 ] (1b) 32 were prepared according to the reported methods. Other reagents were used as received.…”

“…Using this method, a diruthenium tetrahydrido complex, [(Cp ‡ Ru) 2 (μ-H) 4 ] (1b, Cp ‡ = 1,2,4-C 5 H 2 t Bu 3 ), was obtained in 98% yield from [Cp ‡ RuCl 2 ] 2 . 32 The yield of 1b was dramatically improved in comparison to the reaction of this same complex with LiAlH 4 , presumably due to the suppression of undesired side reactions by the aluminum compounds formed upon protonolysis.…”

“…However, this method is restricted to the cases where the individual starting polyhydrido complexes are readily available and are stable enough to be handled under normal conditions. − As an alternative method, we recently reported the direct synthesis of polyhydride clusters from metal halides via gentle heating in 2-propanol in the presence of a base. Using this method, a diruthenium tetrahydrido complex, [(Cp ‡ Ru) 2 (μ-H) 4 ] ( 1b , Cp ‡ = 1,2,4-C 5 H 2 t Bu 3 ), was obtained in 98% yield from [Cp ‡ RuCl 2 ] 2 . The yield of 1b was dramatically improved in comparison to the reaction of this same complex with LiAlH 4 , presumably due to the suppression of undesired side reactions by the aluminum compounds formed upon protonolysis.…”