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

Abstract

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.

Forging Ru–Csp2 Bonds in Paddlewheel Complexes Using the Lithium–Halogen Exchange Reaction

“…2.33 Å). This is attributed to the underestimation of Ru–Ru interactions by the B3LYP functional . On the other hand, the optimized Ru–C bond lengths (ca.…”

“…This is attributed to the underestimation of Ru−Ru interactions by the B3LYP functional. 36 On the other hand, the optimized Ru−C bond lengths (ca. 2.17 Å for 1′ and 2.19 Å for 6′) are shorter than the experimental values (ca.…”

Imidazopyridine-fused [1,3]diazepinones: modulations of positions 2 to 4 and their impacts on the anti-melanoma activity

“…These latter were then oxidised using manganese (II) oxide to generate 4-benzoyl-benzaldehyde 25 and quinoline-6-carbaldehyde 26. For compound 4 0 bearing an alkyne group, the TMS protected 4-formylphenylacetylene 27 was prepared from 4-bromobenzaldehyde, using a Sonogahira reaction, according to the procedure described by Cummings et al (Scheme 3) 24 . Boc protecting-3-indolecarboxaldehyde 28 was prepared from 3-indolecarboxaldehyde and di-tertbutyl dicarbonate, using the procedure described by Pelcman et al (Scheme 3) 25 .…”

Electron Delocalization and FeII → Ru2 Metal-to-Metal Charge Transfer Properties in Diruthenium-Based Compounds

“…The investigation on mixed valence complexes has attracted great attention from chemists because such complexes can serve as excellent systems for the investigations of electron transfer existed in the nature and may be potential in molecular electronics, − molecular magnetism, − molecular conductors, nonlinear optical materials, , and so on. − Diruthenium paddlewheel compounds distinguish themselves with the rich redox characteristics and a remarkable range of accessible oxidation states from Ru 2 (I,II) to Ru 2 (III,IV) and the intricate manifolds of electronic configurations of M–M, which are also easily oxidized and can be good potential electron acceptors to study electron transfer. , There has been a lot of interest in incorporating diruthenium paddlewheel compounds into various supramolecule to design electron delocalization molecules and explore their potential applications as molecular wires. − Meanwhile, because of the excellent electron transfer promoting and coordinating ability of the cyanide bridge, cyanido-bridged MV complexes occupy an important position in the investigation of electron transfer and electronic coupling. − …”