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Ru(0)-azoimine-carbonyl and Ru(II)-pyridyl-azo-imidazole complexes

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Title: Ru(0)-azoimine-carbonyl and Ru(II)-pyridyl-azo-imidazole complexes
Authors: Mathur, T.1, Dinda, J.1, Datta, P.1, Mostafa, G.1, Lu, T.-H.2, Sinha, C.1 c_r_sinha@yahoo.com
Source: Polyhedron. Sep2006, Vol. 25 Issue 13, p2503-2512. 10p.
Subjects: Physical & theoretical chemistry, Imidazoles, Alcohol, Optical polarization
Abstract: Abstract: The reaction of 2-(3′-pyridylazo)imidazole (3′-PyaiH) or its 1-alkyl derivative, 3′-PyaiR, with Ru(CO)3(PPh3)2 has synthesized air stable, moisture insensitive, diamagnetic Ru(0) complexes, [Ru(CO)(3′-PyaiR)(PPh3)2]. The ligands serve as an unsymmetric N,N′-chelating agent (N(imidazole) and N(azo) are abbreviated as N and N′, respectively). The X-ray structure determination of [Ru(CO)(3′-PyaiH)(PPh3)2] shows a square pyramidal geometry. The square plane is made up of Ru, 2P, C(O), N(1), and with N(3) at the apex. Other spectroscopic studies (IR, UV–Vis, NMR) support the stereochemistry. Electrochemistry shows three consecutive anodic peaks (E pa) and suggest irreversible redox responses of Ru(I)/Ru(0), Ru(II)/Ru(I), Ru(III)/Ru(II) and azo reductions. Oxidation by Cl2 of [Ru(CO)(3′-PyaiR)(PPh3)2] has isolated the Ru(II)-complex as the perchlorate salt, [Ru(CO)(Cl)(3′-PyaiR)(PPh3)2](ClO4). A solution of RuCl3 and 3′-PyaiR in ethanol has isolated two isomers of the composition Ru(3′-PyaiR)2Cl2. They have been characterized by spectral and electrochemical data. [Copyright &y& Elsevier]
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Abstract:Abstract: The reaction of 2-(3′-pyridylazo)imidazole (3′-PyaiH) or its 1-alkyl derivative, 3′-PyaiR, with Ru(CO)3(PPh3)2 has synthesized air stable, moisture insensitive, diamagnetic Ru(0) complexes, [Ru(CO)(3′-PyaiR)(PPh3)2]. The ligands serve as an unsymmetric N,N′-chelating agent (N(imidazole) and N(azo) are abbreviated as N and N′, respectively). The X-ray structure determination of [Ru(CO)(3′-PyaiH)(PPh3)2] shows a square pyramidal geometry. The square plane is made up of Ru, 2P, C(O), N(1), and with N(3) at the apex. Other spectroscopic studies (IR, UV–Vis, NMR) support the stereochemistry. Electrochemistry shows three consecutive anodic peaks (E pa) and suggest irreversible redox responses of Ru(I)/Ru(0), Ru(II)/Ru(I), Ru(III)/Ru(II) and azo reductions. Oxidation by Cl2 of [Ru(CO)(3′-PyaiR)(PPh3)2] has isolated the Ru(II)-complex as the perchlorate salt, [Ru(CO)(Cl)(3′-PyaiR)(PPh3)2](ClO4). A solution of RuCl3 and 3′-PyaiR in ethanol has isolated two isomers of the composition Ru(3′-PyaiR)2Cl2. They have been characterized by spectral and electrochemical data. [Copyright &y& Elsevier]
ISSN:02775387
DOI:10.1016/j.poly.2006.02.018