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Correspondence of RuIIIRuII and RuIVRuIII Mixed Valent States in a SmallDinuclear Complex
2012 (English)In: Chemistry - A European Journal, ISSN 0947-6539, E-ISSN 1521-3765, Vol. 18, 5667-5675 p.Article in journal (Refereed) Published
Abstract [en]

The dirutheniumACHTUNGTRENUNG(III) compound[(m-oxa){RuACHTUNGTRENUNG(acac)2}2] [1, oxa2=oxamidato(2), acac=2,4-pentanedionato]exhibits an S=1 ground statewith antiferromagnetic spin-spin coupling(J=40 cm1). The molecularstructure in the crystal of 1·2C7H8 revealedan intramolecular metal–metaldistance of 5.433 and a notableasymmetry within the bridging ligand.Cyclic voltammetry and spectroelectrochemistry(EPR, UV/Vis/NIR) of thetwo-step reduction and of the two-stepoxidation (irreversible second step)produced monocation and monoanionintermediates (Kc=105.9) with broadNIR absorption bands (e ca.2000m1cm1) and maxima at 1800 (1)and 1500 nm (1+). TD-DFT calculationssupport a RuIIIRuII formulationfor 1 with a doublet ground state. The1+ ion (RuIVRuIII) was calculated withan S=3/2 ground state and the doubletstate higher in energy (DE=694.6 cm1). The Mulliken spin densitycalculations showed little participationof the ligand bridge in the spin accommodationfor all paramagnetic species[(m-oxa){RuACHTUNGTRENUNG(acac)2}2]n, n=+1, 0, 1,and, accordingly, the NIR absorptionswere identified as metal-to-metal (intervalence)charge transfers. Whereasonly one such NIR band was observedfor the RuIIIRuII (4d5/4d6) system 1,the RuIVRuIII (4d4/4d5) form 1+ exhibitedextended absorbance over the UV/Vis/NIR range.

Place, publisher, year, edition, pages
2012. Vol. 18, 5667-5675 p.
National Category
Inorganic Chemistry
Research subject
Chemistry with specialization in Inorganic Chemistry
URN: urn:nbn:se:uu:diva-236122DOI: 10.1002/chem.201103618OAI: oai:DiVA.org:uu-236122DiVA: diva2:762767
Available from: 2014-11-12 Created: 2014-11-12 Last updated: 2014-11-12

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