Phosphorous Acid and Arsenious Acid as Ligands

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 Mo3MQ4 4+ core (M = Ni, Pd; Q = S, Se)

“…The ease of oxidation of the HP(OH) 2 molecule coordinated to the palladium atom did not allow us to isolate the cor responding complex as the solid phase; instead, the [Mo 3 (Pd(P(OH) 3 ))S 4 (H 2 O) 6 Cl 3 ] + complex crystallized as a supramolecular adduct with cucurbit [6]uril. 1 The ability of palladium black to catalyze H 3 PO 2 oxidation by pro tons in acidic solution has long been known. 6 Hence, it can be hypothesized that this heterogeneous process in volves chemosorption of HP(OH) 2 on the particle surface of palladium black followed by oxidation.…”

“…These complexes induce isomerization of phos phorous acid (HO) 2 P(O)H, hypophosphorous acid (HO)P(O)H 2 , and the phenyl substituted derivatives Ph 2 P(O)H and PhP(O)(OH)H to form the correspond ing hydroxo tautomers (>P-OH), which are stabilized by coordination to the heterometal atom (palladium or nickel) due to involvement of the lone electron pair of the phosphorus atom that becomes free. [1][2][3][4] The for mation of the [Mo 3 (Pd(P(OH) 3 ))S 4 (H 2 O) 6 Cl 3 ] + and [W 3 (Ni(HP(OH) 2 )Se 4 (H 2 O) 9 ] 4+ complexes was estab lished by 31 P NMR spectroscopy and X ray diffraction. 1, 2 The formation of the [Mo 3 (Pd(PhP(OH) 2 ))S 4 (H 2 O) 9 ] 4+ and [Mo 3 (Pd(Ph 2 P(OH))S 4 (H 2 O) 9 ] 4+ complexes was proved by 31 P NMR spectroscopy.…”

A New Series of Homologous Cluster Complexes [Mo3(M'EPh3)Q4Cl4(H2O)5] (M' = Ni, Pd; E = P, As, Sb; Q = S, Se)

“…[2] The Mo 3 PdS 4 4+ clusters catalyze nucleophilic addition to alkynes [3] and [Mo 3 NiS 4 (H 2 O) 10 ] 4+ has proved to be efficient in various heterogeneous catalytic processes. [4,5] Recently it was found that the heterometal in M 3 MЈS 4 4+ clusters (M = Mo, W; heterometal (MЈ) = Ni, Pd) stabilize very labile molecules of P(OH) 3 , RP(OH) 2 (R = H, Ph) and Ph 2 P(OH) by coordination at phosphorus [6][7][8] . Nonlinear optical properties of [M 3 (CuX)Q 4 (dmpe) 3 X 3 ]PF 6 (M = Mo, W; X = Cl, Br; Q = S, Se) were also studied.…”

Coordination of Phenylsulfinate PhSO2— to Mo3MS44+ Clusters (M = Ni, Pd)

“…A Mo 3 Pd cluster, [Mo 3 (PdCl)S 4 (tacn) 3 ](PF 6 ) 3 catalyzes the stereoselective addition of alcohols and carboxylic acids to acetylenes with electron-withdrawing groups [2,6]. We [11].…”