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Structural and spectroscopic properties of Ru(II) complexes of 4-(aryl)thiosemicarbazones of thiophen-2-carbaldehyde

Naskar, S., Naskar, S., Drew, M.G.B., Gorelsky, S.I., Lassalle-Kaiser, B., Aukauloo, A., Mishra, D. and Chattopadhyay, S.K. (2009) Structural and spectroscopic properties of Ru(II) complexes of 4-(aryl)thiosemicarbazones of thiophen-2-carbaldehyde. Polyhedron, 28 (18). pp. 4101-4109. ISSN 0277-5387

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To link to this item DOI: 10.1016/j.poly.2009.09.030

Abstract/Summary

Six Ru(II) complexes of formula [Ru(L)(2)(PPh3)(2)] have been prepared where LH = 4-(aryl)thiosemicarbazones of thiophen-2-carbaldehyde. X-ray crystal structures of five of the complexes are reported. In all the complexes ruthenium is six coordinate with a distorted octahedral cis-P-2, cis-N-2, trans-S-2 donor environment, and each of the two thiosemicarbazone ligands are coordinated in a bidentate fashion forming a four membered chelate ring. The complexes undergo a one-electron oxidation at similar to 0.5 V vs. Ag/AgCl. The EPR spectrum of the electrochemically oxidized solution at 100 K shows a rhombic signal, with transitions at g(1) = 2.27, g(2) = 2.00 and g(3) = 1.80. DFT calculations on one of the complexes suggest that there is 35% ruthenium and 17% sulfur orbital contribution to the HOMO. These results suggest that the assignment of metal atom oxidation states in these compounds is not unambiguous. (C) 2009 Elsevier Ltd. All rights reserved.

Item Type:Article
Refereed:Yes
Divisions:Faculty of Life Sciences > School of Chemistry, Food and Pharmacy > Department of Chemistry
ID Code:11527
Uncontrolled Keywords:Thiosemicarbazones, Thiophen-2-carbaldehyde, Ru(II) thiosemicarbazone complexes, X-ray crystal structure, EPR, DFT calculations , TRANSITION-METAL COMPLEXES, N-S DONORS, CRYSTAL-STRUCTURE, RUTHENIUM COMPLEXES, THIOSEMICARBAZONE COMPLEXES, REDOX PROPERTIES, ELECTROCHEMICAL PROPERTIES, PLATINUM(II) COMPLEXES, LIGATIONAL BEHAVIOR, SPECTRAL PROPERTIES

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