Oxidative dehydrogenation on the α-carbon of 4-pyridylacetonitrile complexes of pentaammineruthenium(II)

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Title:	Oxidative dehydrogenation on the α-carbon of 4-pyridylacetonitrile complexes of pentaammineruthenium(II)
Authors:	Liu, S.a, Lee, S.a, Wang, S.a, Yeh, A.a, Gau, H.-M.b, Shao, M.-Y.b
Contributors:	Department of Chemistry, Tunghai University
Date:	2001
Issue Date:	2013-05-14T09:01:30Z (UTC)
Abstract:	The oxidation of Ru(NH 3) 5NCCH 2py 2+ in 0.10 M HCl turns the solution from yellow to greenish blue with an absorption at λ = 791 nm. The absorbance reaches its maximum value when the complex undergoes a two-electron oxidation. The IR and 1H NMR spectra of the product indicate that the metal center remains as Ru(II) and that the ligand is oxidized. The 13C NMR spectral results suggest that the oxidation product is [(NH 3) 5RuNCC(pyH)C(pyH)CNRu (NH 3) 5](ClO 4) 6. Cyclic voltammetry of the product solution also indicates that the oxidation proceeds in two one-electron steps corresponding to [Ru(III),Ru(II)] + e - ? [Ru(II),Ru(II)] and [Ru(III),Ru(III)] + e - ? [Ru(III),Ru(II)]. The structure of the product in deprotonated form [(NH 3) 5RuNCC(py)C(py)CNRu (NH 3) 5](ClO 4) 4 (H 2O) 2 was determined crystallographically. [(NH 3) 5RuNCC(py)C(py)CNRu (NH 3) 5](ClO 4) 4 (H 2O) 2 crystallizes in the orthorhombic Pbca space group with cell constants a = 13.7138 (16) ?, b = 15.7553 (18) ?, c = 17.831 (2) ?, and Z = 4. A mechanism for the oxidation has been proposed on the basis of the kinetic studies in the region of 0.01-0.20 M acid concentrations.
Relation:	Inorganic Chemistry Volume 40, Issue 24, 19 November 2001, Pages 6139-6143
Appears in Collections:	[化學系所] 期刊論文

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