Diruthenium(III,III) ethynyl-phenyleneimine molecular wires: preparation via on-complex Schiff base condensation.
The diruthenium compound trans-Ru(2)(DMBA)(4)(C≡C-C(6)H(4)-4-CHO)(2) (1; DMBA is N,N'-dimethylbenzamidinate) was prepared from the reaction between Ru(2)(DMBA)(4)(NO(3))(2) and HC≡C-C(6)H(4)-4-CHO under the weak base conditions. The aldehyde groups of 1 undergo a condensation reaction with NH(2)C(6)H(4)-4-Y (Y = H and NH(2)) to afford new compounds trans-Ru(2)(DMBA)(4)(C≡C-C(6)H(4)-4-CH═N-C(6)H(4)-4'-Y)(2) (Y = H (2) and NH(2) (3)). A related compound, Ru(2)(DMBA)(4)(C≡C-C(6)H(4)-4-N═C(Me)Fc)(2) (4), was also prepared from the reaction between Ru(2)(DMBA)(4)(NO(3))(2) and HC≡C-C(6)H(4)-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 Fc 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.
Department of Chemistry, Purdue University, West Lafayette, Indiana 47907, USA.
Steven P
SP
Cummings
Zhi
Z
Cao
Phillip E
PE
Fanwick
Anastasia
A
Kharlamova
Tong
T
Ren
D000480:Alkynes / Q000737:chemistry*; D004563:Electrochemistry; D007097:Imines / Q000737:chemistry*; D008958:Models, Molecular; D015394:Molecular Structure; D009942:Organometallic Compounds / Q000138:chemical synthesis* / Q000737:chemistry; D011789:Quantum Theory; D012428:Ruthenium / Q000737:chemistry*; D012545:Schiff Bases / Q000737:chemistry*
D000480:Alkynes; D007097:Imines; D009942:Organometallic Compounds; D012545:Schiff Bases; D012428:Ruthenium