Journal
INORGANIC CHEMISTRY
Volume 54, Issue 7, Pages 3376-3386Publisher
AMER CHEMICAL SOC
DOI: 10.1021/ic503070j
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Funding
- Department of Science and Technology, Council of Scientific and Industrial Research, New Delhi (India)
- DAAD
- FCI
- DFG (Germany)
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The compounds Ru(acac)(2)(Q) (1), [Ru(bpy)(2)(Q)](ClO4)(2) ([2](ClO4)(2)), and [Ru(pap)(2)(Q)]PF6 ([3]PF6), containing Q = N,N'-diphenyl-o-benzoquinonediimine and donating 2,4-pentanedionate ligands (acac), pi-accepting 2,2/-bipyridine (bpy), or strongly pi-accepting 2-phenylazopyridine (pap) were prepared and structurally identified. The electronic structures of the complexes and several accessible oxidized and reduced forms were studied experimentally (electrochemistry, magnetic resonance, ultraviolet-visible-near-infrared (UV-vis-NIR) spectroelectrochemistry) and computationally (DFT/TD-DFT) to reveal significantly variable electron transfer behavior and charge distribution. While the redox system 1+1 prefers trivalent ruthenium with corresponding oxidation states Q(0)-Q(2-) of the noninnocent ligand, the series 2(2+)-2(0) and 3(2+)-3(-) retain Ru-II. The bpy and pap co-ligands are not only spectators but can also be reduced prior to a second reduction of Q. The present study with new experimental and computational evidence on the influence of co-ligands on the metal is complementary to a report on the substituent effects in o-quinonediimine ligands [Kalinina et al., Inorg. Chem. 2008, 47, 10110] and to the discussion of the most appropriate oxidation state formulation Ru-II(Q(0)) or Ru-III(Q(.-)).
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