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|Title: ||Reductive Approach to Mixed Valency (n=1-) in the Pyrazine Ligand-Bridged [(acac)(2)Ru(mu-L(2-))Ru(acac)(2)](n) (L(2-)=2,5-Pyrazine-dicarboxylate) through Experiment and Theory|
|Authors: ||DAS, A|
DINUCLEAR RUTHENIUM COMPLEXES
|Issue Date: ||2011|
|Publisher: ||AMER CHEMICAL SOC|
|Citation: ||INORGANIC CHEMISTRY,50(15)7040-7049|
|Abstract: ||The diruthenium(III) complex [(acac)(2)Ru(mu-L(2-))Ru(acac)(2)] (1) with acac(-) = acetylacetonato = 2,4-pentanedionato and a 2,5-pyrazine-dicarboxylato bridge, L(2-), has been obtained and structurally characterized as the rac (Delta Delta,Lambda Lambda) diastereomer. The Ru(III)Ru(III) configuration in 1 (d(Ru-au) = 6.799 angstrom) results in a triplet ground state (mu = 2.82/2 mu(B) at 300 K) with a density functional theory (DFT) calculated triplet-singlet gap of 10840 cm-and the metal ions as the primary spin-bearing centers (Mulliken spin densities: Ru, 1.711; L, 0.105; acac, 0.184). The paramagnetic 1 exhibits :broad, upfield shifted (1)H NMR signals with delta values ranging from -10 to -65 -65 ppm and an anisotropic electron paramagnetic resonance (EPR), spectrum (< g > = 2.133, g(1) - g(3) = Delta g = 0.512), accompanied by a weak half-field signal at g = 4.420 in glassy frozen acetonitrile at 4 K Compound 1 displays two closely spaced oxidation steps to yield labile cations. In contrast, two well separated reversible reduction steps of 1 signify appreciable electrochemical metal-metal interaction in the Run Rum mixed-valent state 1(-) (K(c) approximate to 10(7)). The intermediate 1(-) shows a weak, broad Ru(II)-> Ru(III) intervalence charge transfer (IVCT) band at about 1040 nm (epsilon = 380 M(-1) cm(-1)); the DFT approach for 1(-) yielded Mulliken spin densities of 0.460 and 0.685 for the two metal centers. The monitoring of the frequencies of the uncoordinated C=O groups of L(2-) in 1" by IR spectroelectrochemistry suggests valence averaging (Ru(2.5)Ru(2.5)) in 1(-) on the vibrational time scale. The mixed-valent 1(-) displays a rhombic EPR signal (< g > = 2.239 and Delta g = 0.32) which reveals non-negligible contributions from the bridging ligand, reflecting a partial hole-transfer mechanism and being confirmed by the DFT-calculated spin distribution (Mulliken spin density of -0.241 for L in 1(-)). The major low energy electronic transitions in 1(n) (n = 0,-,2-) have been assigned as charge transfer processes with the support of TD-DFT analysis.|
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