Diruthenium(III,III) Ethynyl-phenyleneimine Molecular Wires: Preparation via On-Complex Schiff Base Condensation

作者：Cummings Steven P; Cao Zhi; Fanwick Phillip E; Kharlamova Anastasia; Ren Tong^*

来源：Inorganic Chemistry, 2012, 51(14): 7561-7568.

DOI：10.1021/ic300182h

The diruthenium compound trans-Ru-2(DMBA)(4)(C C-C6H4-4-CHO)(2) (1; DMBA is N,N'-dimethylbenzamidinate) was prepared from the reaction between Ru-2(DMBA)(4)(NO3)(2) and HC C-C6H4-4-CHO under the weak base conditions. The aldehyde groups of 1 undergo a condensation reaction with NH2C6H4-4-Y (Y = H and NH2) to afford new compounds trans-Ru-2(DMBA)(4)(C C-C6H4-4-CH=N C6H4-4'-Y)(2) (Y = H (2) and NH2 (3)). A related compound, Ru-2(DMBA)(4)(C C-C6H4-4-N=C(Me)Fc)(2) (4), was also prepared from the reaction between Ru-2(DMBA)(4)(NO3)(2) and HCC C6H4-N=C(Me)Fc. X-ray structural studies of compounds 1 and 2 revealed significant deviation from an idealized D-4h geometry in the coordination sphere of the Ru-2 core. Voltammetric measurements revealed four one electron redox processes for compounds 1-3: the Ru-2 centered oxidation and reduction, and a pair of reductions of the imine or aldehyde groups. Compound 4 displays an additional oxidation attributed to the Fe groups. DFT calculations were performed on model compounds to gain a more thorough understanding of the interaction of the organic functional groups across the diruthenium bridge.

• 出版日期2012-7-16