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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- Sokolov, M.N., Chubarova, E.V., Kovalenko, K.A. et al. Russ Chem Bull (2005) 54: 615. doi:10.1007/s11172-005-0296-1
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 uril, and the [Mo3(Ni(P(OH)3))S4(H2O)8Cl]3+ complex was isolated as an adduct with cucurbit uril. The structures of both compounds were established by X-ray diffraction analysis.