Stabilization of tautomeric forms P(OH)3 and HP(OH)2 and their derivatives by coordination to palladium and nickel atoms in heterometallic clusters with the Mo3MQ44+ core (M = Ni, Pd; Q = S, Se) |
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| Authors: | M N Sokolov E V Chubarova K A Kovalenko I V Mironov A V Virovets E V Peresypkina and V P Fedin |
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| Institution: | (1) A. V. Nikolaev Institute of Inorganic Chemistry, Siberian Branch of the Russian Academy of Sciences, 3 prosp. Akad. Lavrentieva, 630090 Novosibirsk, Russian Federation |
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| Abstract: | The cluster aqua complexes Mo3(MCl)Q4(H2O)9]3+ (M = Pd or Ni) in hydrochloric acid solutions induce isomerization of the hydrophosphoryl compounds (HO)2P(O)H, (HO)P(O)H2, PhP(O)(OH)H, and Ph2P(O)H into the hydroxo tautomers P(OH)3, HP(OH)2, PhP(OH)2, and Ph2P(OH), which are stabilized by coordination of the phosphorus atom to the Pd or Ni atoms. The reactions were studied by 31P NMR and UV-Vis spectroscopy. The kinetics of the reactions of phosphorous acid with Mo3(PdCl)Q4(H2O)9]3+ was investigated by spectrophotometry. The Mo3(Pd(PhP(OH)2))S4(H2O)2Cl7]3− complex was isolated as a supramolecular adduct with cucurbit 8]uril, and the Mo3(Ni(P(OH)3))S4(H2O)8Cl]3+ complex was isolated as an adduct with cucurbit 6]uril. The structures of both compounds were established by X-ray diffraction analysis.__________Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 3, pp. 606–613, March, 2005. |
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| Keywords: | molybdenum palladium chalcogenide clusters cucurbituril phosphorus acids |
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