A new diruthenium compound trans-[Ru2(DMBA)4](C=C-C6H4-4-CHO)2 (1 ;  DMBA is N,N'-dimethoxybenzaminidnate) was prepared from the reaction between Ru2(DMBA)4(NO3)2 and HC=C-C6H4-4-CHO under weak base conditions. The aldehyde groups in 1  underwent a condensation reaction with NH2C6H4-4-Y (Y = H and NH2) to afford new compounds trans-[Ru2(DMBA)4](C=C-C6H4-4-CH=N-C6H4-4'-Y)2 (2 , Y = H; 3 , Y = NH2). A related compound, Ru2(DMBA)4-(C=C-C6H4-4-N=C(Me)Fc)2 (4 ), was also prepared from the reaction between Ru2(DMBA)4(NO3)2 and HC=C-C6H4-N=C(Me)Fc.  X-ray structural studies of compounds 1  and 2  revealed significant deviation from an idealized D4h geometry in the coordination sphere of the Ru2 core.  Voltammetric measurements indicated that compounds 1-3  display four, one-electron redox processes: an oxidation of Ru2, a reduction of Ru2, and a stepwise reduction of the imine groups. Compound 4  displays an additional oxidation attributed to the Fc moiety.  DFT calculations were performed on model compounds to gain a more thorough understanding of the stepwise reduction of the imine group.

Diruthenium [sigma]-iminophenylacetylide complexes from on-complex Schiff base condensation

243rd National Meeting (2012)

The official archive and repository for all ACS Meetings & Expositions abstracts and select posters or presentations.