Formation of polynuclear palladium complexes with the benzimidazole-2-thiolate anion |
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Authors: | M O Talismanova A A Sidorov G G Aleksandrov V N Charushin S K Kotovskaya V P Ananikov I L Eremenko I I Moiseeva |
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Institution: | (1) N. S. Kurnakov Institute of General and Inorganic Chemistry, Russian Academy of Sciences, 31 Leninsky prosp., 119991 Moscow, Russian Federation;(2) I. Ya. Postovsky Institute of Organic Synthesis, Ural Branch of the Russian Academy of Sciences, 20 ul. S. Kovalevskoi, 620041 Ekaterinburg, Russian Federation;(3) N. D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences, 47 Leninsky prosp., 119991 Moscow, Russian Federation |
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Abstract: | The reactions of palladium(II) salts with 2-mercaptobenzimidazole (HL) and its 5,6-difluorinated derivative (HLF) were investigated. In the presence of hydrochloric acid, PdCl2 and K2PdCl4 react with HL and HLF in the ethanol—water and acetonitrile—water systems to form the mono-nuclear dicationic complexes Pd(HL)4]Cl2 (1) and Pd(LF)4]Cl2 (2). In the absence of HCl, the reactions afford the tetranuclear complex Pd4(L)2(μ3-S,N-(L))2(μS,N-(L))4] (3). The reaction of triethylamine with an ethanolic solution of 3 leads to degradation of 3 and the formation of the lantern-type dinuclear complex Pd2(μ2-(L)4] (4), in which the palladium atoms are in the nonequivalent coordination environment, PdN4 and PdS4. The reaction of K2PdCl4 with HL or HLF in the THF—water or acetonitrile—water systems (for the reaction with HLF) in the presence of Et3N produces the lantern-type dinuclear complexes Pd2(μS,N′-(L3))4] and Pd2(μ-S,N′-(LF))4] (5), in which the metal atoms are in the equivalent coordination environment (cis-PdN2S2).
Dedicated to Academician G. A. Tolstikov on the occasion of his 75th birthday.
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 1, pp. 45–52, January, 2008. |
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Keywords: | 2-mercaptobenzimidazole palladium(II) complexes polynuclear complexes nuclear magnetic resonance X-ray diffraction analysis |
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