Modified synthesis of mixed-ligand dinuclear Ru-Ir, Ru-Rh, and Ru-Ru polyhydride-bridged complexes, CpsRuH(3)ML (Cps = C5Me5 (Cp*), (C5Bu3H2)-Bu-t (Cp double dagger); M = Rh, Ir, Ru; L = C-5(CH3)(5), C6H6, p-CH3C6H4CH(CH3)(2))

作者：Shimogawa Ryuichi; Takao Toshiro^*; Suzuki Hiroharu

来源：Journal of Organometallic Chemistry, 2016, 818: 168-178.

DOI：10.1016/j.jorganchem.2016.06.011

• Ruthenium
• Rhodium
• Iridium
• Hydride
• Hetero-bimetallic cluster

Hetero-bimetallic polyhydride clusters exhibit a regio-and chemoselective activation of a substrate. The rational synthetic method for hetero-bimetallic polyhydride complexes using readily available halide complexes is reported. The reaction of hetero-bimetallic RueIr trichloride complex, Cp*Ru(mu-Cl)(3)IrCp* (5a), in 2-propanol in the presence of a base afforded Cp*Ru(mu-H)(3)IrCp* (6a) by sequential salt metathesis and beta-hydrogen elimination. CpsRu(mu-H)(3)ML [Cps = Cp*, Cpz; ML = IrCp*, RhCp*, Ru(p-cymene), Ru(benzene)] were also selectively synthesized by reacting a mixture of CpsRuCl/(n) and [LM(mu-Cl)Cl](2) via the formation of CpsRu(mu-Cl)(3)ML. The IrCp*, RhCp*, and Ru(arene) complexes, Cp double dagger Ru(mu-H)(3)IrCp* (6b), Cp double dagger Ru(mu-H)(3)RhCp* (8), and Cp double dagger Ru(mu-H)(3)Ru(arene) (10), were newly synthesized by this method. The reaction mechanism was discussed based on the hetero-bimetallic chloro-hydride intermediates. Absence of main group hydride reagents was responsible for maintaining the hetero-bimetallic structure during the introduction of the hydride ligand, which lead to selective formation of dinuclear mixedmetal trihydride-bridged complexes.

• 出版日期2016-9-1