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)

  title={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)},
  author={Maxim N. Sokolov and Elena V. Chubarova and Konstantin A. Kovalenko and Igor V. Mironov and Alexander V Virovets and Eugenia V Peresypkina and Vladimir P. Fedin},
  journal={Russian Chemical Bulletin},
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… 
10 Citations
Synthesis, structure and reactivity of cuboidal-type cluster aqua complexes with W3PdS44+ core
The reaction of PdCl2 with [W3S4(H2O)9]4+ in the presence of hypophosphorous acid in 2 M HCl gives cuboidal cluster [W3(PdCl)S4(H2O)9]3+ (1) which undergoes condensation and crystallises from Hpts
Kinetic, DFT and TD-DFT studies on the mechanism of stabilization of pyramidal H3PO3 at the [Mo3M'S4(H2O)10]4+ clusters (M' = Pd, Ni).
DFT calculations indicate that tautomerization of H(3)PO(3), both processes being less favored at the Ni cluster than at its Pd analogue, involves essentially ligand-to-metal charge-transfer (LMCT) transitions.
Synthesis, characterization, X-ray crystallography and stability in aqueous medium of trans -[Ru(CO)(NH 3 ) 4 P(OH) 3 ] 2+
Abstract Here, we report the synthesis, characterization, crystal data and DFT calculation of a new water-soluble ruthenium(II) carbonyl complex. The trans-[Ru(CO)(NH3)4P(O)(OH)2]Cl is a robust
Combined kinetic and DFT studies on the stabilization of the pyramidal form of H3PO2 at the heterometal site of [Mo3M'S4(H2O)10]4+ clusters (M' = Pd, Ni).
The major finding is that the role of the additional H(3)PO(2) molecule in the second step consists in catalysing a hydrogen shift from phosphorus to oxygen in O-coordinated H( 3) PO(2), which is made possible by its capability of accepting a proton from P-H to form H(4)PO (2)(+) and then transfer it to the oxygen.
Coordination Properties of Perfluoroethyl- and Perfluorophenyl-Substituted Phosphonous acids, R(f)P(OH)2.
The catalytic activity of the palladium complexes in the Suzuki cross-coupling reaction between 1-bromo-3-fluorobenzene and phenyl boronic acid was demonstrated.
Unprecedented solvent-assisted reactivity of Hydrido W3CuS4 cubane clusters: the non-innocent behaviour of the cluster-core unit.
A mechanism for the substitution reaction is proposed in which attack at the copper centre by acetonitrile or water causes disruption of the cubane-type core and this kind of process is unprecedented in the chemistry of M(3)M'Q(4) (M=Mo, W; Q=S, Se) clusters.
P(═O)H to P-OH Tautomerism: A Theoretical and Experimental Study.
A combined theoretical and experimental study of the initial tautomerization rate of a range of phosphinylidene compounds establishes a quantitative measure for the reactivity of various phosphorus compounds, as well as an accurate predictive tool.
Catalytic effect of a second H3PO2 in the mechanism of stabilisation of the unstable pyramidal tautomer of H3PO2 coordinated at [Mo3S4M'] clusters (M' = Ni, Pd).
Kinetic and DFT studies indicate that the stabilization of a single pyramidal H(3)PO(2) molecule at the M' site of [Mo(3)S(4)M'] clusters requires the participation of two tetrahedral H(3)PO(2)
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Reactivity of Mo3PdS4+4 Cluster: Evidence for New Ligands PhP(OH)2 and Ph2P(OH) and Structural Characterization of [Mo3(Pd(PPh3))S4(H2O)5Cl4]⋅0.5CH3OH⋅3H2O
Cuboidal cluster aqua complex [Mo3(PdCl)S4(H2O)9]3+ in 4M HCl causes isomerization of (HO)2P(O)(H), (HO)P(O)(H)2, PhP(O)(OH)(H), and Ph2P(O)(H) into hydroxo tautomers P(OH)3, HP(OH)2, PhP(OH)2, and
Coordination of Phenylsulfinate PhSO2— to Mo3MS44+ Clusters (M = Ni, Pd)
Reaction of heterometal cuboidal clusters [Mo3(MCl)S4(H2O)9]3+ (M = Ni, Pd) with PhSO2Na in aqueous HCl leads to the substitution at Ni or Pd to give the [Mo3(M(PhSO2))(H2O)9—xClx](3—x)+species,
Stabilization of the previously unknown tautomer HP(OH)2 of hypophosphorous acid as ligand; preparation of [W3(Ni(HP(OH)2))Q4(H2O)9]4+ (Q = S, Se) complexes.
Bis(hydroxy)phosphine, the isomer of hypophosphorous acid which remained elusive for a long time, coordinates to the Ni site of heterometallic clusters with a W3NiQ4 core (Q = S, Se) to give
Ligand Substitution Reactions at the Nickel of [Mo(3)NiS(4)(H(2)O)(10)](4+) with Two Water Soluble Phosphines, CO, Br(-), I(-), and NCS(-) and the Inertness of the 1,4,7-Triazacyclononane (L) Complex [Mo(3)(NiL)S(4)(H(2)O)(9)](4+).
Stopped-flow formation rate constants for six X reagents, including two water soluble air-stable phosphines, 1,3,5-triaza-7-phosphaadamantane PTA and tris(3-sulfonatophenyl)phosphine TPPTS(3)(-) (58), and CO (8900) are obtained, consistent with an I(d) dissociative interchange mechanism.
Aqueous Solution Chemistry of the Mo(3)PdS(4) Cube: Substitution Reactions and the Double to Single Cube Interconversion Induced by CO, Two Phosphines, Cl(-), Br(-), and NCS(-).
The kinetics of conversion of an edge-linked double cube to the corresponding single cube has been studied for the first time and can be explained by substitution at nonidentical H(2)O's on each Mo or by the presence of mixed-valent Mo(III)(2)Mo(IV) forms which are sufficiently long-lived to give a kinetic discrimination.
Formation (and properties) of palladium derivatives of [Mo3Q4(H2O)9]4+: absence of similar derivatives of [W3Q4(H2O)9]4+ (Q = S, Se)
The reaction of Pd black with [Mo3Se4(H2O)9]4+ in 2 M HCl gives the single cube [Mo3(PdCl)Se4(H2O)9]3+, which on removal of Cl− forms the edge-linked double cube [{Mo3PdSe4(H2O)9}2]8+. No similar
Gold(I) complexes with PO and P–OH functionalised phosphorus ligands
P-coordination of anionic phosphonite [(R 2 O)R 1 PO] − or phosphite [(RO) 2 PO] − ligands to (triorganophosphine)gold(I) units leads to neutral molecules with an unsymmetrical P–Au–P′ axis and a PO
A new series of homologous cluster complexes [Mo3(M'EPh3)Q4Cl4(H2O)5] (M' = Ni, Pd; E = P, As, Sb; Q = S, Se)
Cluster aqua complexes [Mo3(M'Cl)S4(H2O)9]3+ (M' = Ni, Pd) react with EPh3 (E = P, As, Sb) in HCl/CH3OH to give neutral [Mo3(M'EPh3)S4Cl4(H2O)5] (M' = Pd, E = P (1), E = As (2), E = Sb (3); M' = Ni,
Rhodium complexes with secondary phosphine and phosphinite ligands and the crystal structures of [(PPh2OH)2(PPh2O)Rh(μ-Cl)3Rh(PPh2OH)(PPh2O)2] and [(PPh2OH)(PPh2O)Cl(NCMe)Rh(μ-Cl)2Rh(PPh2OH)(PPh2O)Cl(NCMe)] · 2thf
Abstract RhCl3·3H2O reacts with ca six molar equivalents of PPh2H or PCy2 in EtOH solution under a N2 atmosphere and in the presence of excess NH4PF6 to yield [RhCl2(PPh2H)4]Pf6 or [RhCl2(PCy2H)4]PF6
Cubane-type mixed-metal clusters with molybdenum-nickel-sulfur Mo3NiS4 cores. Syntheses, characterization, and x-ray structures of [Mo3NiS4(H2O)10](CH3C6H4SO3)4.7H2O and Ca2.5[Mo3NiS4(Hnta)(nta)2Cl].14H2O
Reaction of the incomplete cubane-type aqua ion [Mo 3 S 4 (H 2 O) 9 ] 4+ (A) with nickel metal gives a novel cubane-type mixed-metal cluster [Mo 3 NiS 4 (H 2 O) 10 ] 4+ (B') in high yield (75%),