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On the Role of the Bridging Dicyanamidobenzene Ligand in a New Binuclear Ruthenium Complex: [{Ru(tpy)(thd)}2(μ-dicyd)][PF6] with tpy = 2,2‘:6‘,2‘ ‘-Terpyridine and thd = 2,2,6,6-Tetramethyl-3,5-heptanedione
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Section:Abstract
The dicyanamidobenzene-bridge diruthenium complex [{Ru(tpy)(thd)}2(μ-dicyd)][PF6] ([3][PF6]) (dicyd = 1,4-dicyanamidobenzene, tpy = 2,2‘:6‘,2‘ ‘-terpyridine, thd = 2,2,6,6-tetramethyl-3,5-heptanedione) and its mononuclear counterpart [Ru(tpy)(thd)(Ipcyd)] (2) [Ipcyd = 4-iodophenylcyanamide anion (Ipcyd-)] were synthesized and fully characterized. Cyclic voltammetry of 3 showed the presence of four reversible one-electron redox couples. UV−vis−NIR spectroelectrochemistry and EPR spectroscopy of the electrogenerated paramagnetic intermediates were used to ascertain the oxidation-state distribution. The stable starting dinuclear complex 3+ is found to be a ligand-centered anion radical as shown by EPR spectroscopy, magnetic susceptibility measurements, and DFT calculations. Oxidation of 3+ to 32+ led to an EPR silent system due to substantial intramolecular antiferromagnetic interaction of the electron spins carried by the low spin ruthenium(III) atom and the bridging anion radical dicyanamido (dicyd•-), an observation which was supported by UV−vis−NIR, X-ray structure, and DFT calculations. Complex 33+ presented an EPR spectra consistent with a total effective spin S = 1/2 issued from an antiferromagnetic interaction of electron spins carried by two low spin ruthenium(III) atoms and the bridging anion radical dicyd•- in accordance with UV−vis−NIR. This study shows that the dicyanamidobenzene bridging ligand has indubitably a noninnocent behavior.
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This article has been cited by 9 ACS Journal articles (5 most recent appear below).
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- Published In Issue November 13, 2006
- Received June 16, 2006
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