Peroxo-Zr/Hf-containing undecatungstosilicates and -germanates.

A family of dimeric, peroxo-containing heteropolytungstates, [M(2)(O(2))(2)(XW(11)O(39))(2)](12-) [M = Zr(4+), X = Si (1), Ge (2); M = Hf(4+), X = Si (3)], have been synthesized by reacting ZrCl(4)/HfCl(4) with the respective monolacunary Keggin precursor [XW(11)O(39)](8-) (X = Si, Ge) in an aqueous acidic medium (pH 4.8). The isostructural polyanions 1-3 are composed of two (XW(11)O(39)) Keggin units encapsulating a central diperoxo-dimetal fragment {M(2)(O(2))(2)}(4+) (M = Zr(4+), Hf(4+)). Cyclic voltammetry and exhaustive electrolysis studies indicate fast reductive release of the peroxo ligands upon reduction of 1-3. Stoichiometric oxo-transfer studies from 1-3 to the substrate l-methionine were performed, and the reactions were monitored by (1)H NMR.

Copper-, cobalt-, and manganese-containing 17-tungsto-2-germanates.

The sandwich-type tungstogermanates [Cu(3)(H(2)O)(B-beta-GeW(9)O(33)(OH))(B-beta-GeW(8)O(30)(OH))](12-) (1), [Co(H(2)O)(2){Co(3)(B-beta-GeW(9)O(33)(OH))(B-beta-GeW(8)O(30)(OH))}(2)](22-) (2), and [Mn(H(2)O)(2){Mn(3)(H(2)O)(B-beta-GeW(9)O(33)(OH))(B-beta-GeW(8)O(30)(OH))}(2)](22-) (3) were synthesized and characterized by single-crystal X-ray diffraction, elemental analysis, thermogravimetric analysis, and infrared spectroscopy. Polyanion 1 is composed of two nonequivalent Keggin units, (B-beta-GeW(8)O(31)) and (B-beta-GeW(9)O(34)), linked to each other via three copper(II) ions in such a way that there is a plane of symmetry passing through both Ge atoms and the unique Cu atom, resulting in a sandwich-type structure with C(s) symmetry. On the other hand, the monomeric building blocks of 2 and 3 contain the same Keggin fragments as 1, but linked through three octahedrally coordinated Co(2+) or Mn(2+) ions. The major difference between complex 1 and complexes 2 and 3 is that the latter all lack a plane of symmetry due to a different orientation of the rotated triad. Magnetic measurements indicated antiferromagnetic exchange interactions between the three Cu(2+) ions in 1 and between the three Mn(2+) ions in 3. On the other hand, polyanion 2 possesses ferromagnetic interaction of the Co(2+) ions. The best least-squares fit values for 2 are J(z) = 7.9 cm(-1), J(z) = 3.1 cm(-1), J(y) = 2.4 cm(-1), g(z) = 6.77 cm(-1), and g(xy) = 4.15 (R = 2.6 x 10(-2)).

Addition of alkyl radicals to transition-metal-coordinated CO: calculation of the reaction of [Ru(CO)5] and related complexes and relevance to alkane carbonylation.

Electronic structure methods have been used to study the transition state and products of the reaction between alkyl radicals and CO coordinated in transition-metal complexes. At the B3LYP DFT level, methyl addition to a carbonyl of [Ru(CO)5] or [Ru(CO)3(dmpe)] is calculated to be about 6 kcal/mol more exothermic than addition to free CO. In contrast, methyl addition to [Mo(CO)6] is 12 kcal/mol less exothermic than addition to CO, while the reaction enthalpy of methyl addition to [Pd(CO)4] is comparable to that of free CO. Related results are obtained at the CCSD-T level and for the reactions of the cyclohexyl radical. The transition state for these reactions is characterized by significant distortion of the geometry of the reactant complex, which include lengthening and bending of the M-CO bond, but with negligible C-C bond formation. Accordingly, the activation energy for addition to coordinated carbonyls is 2-10 kcal/mol greater than that of addition to free CO. Additional calculations were also carried out on representative unsaturated metal carbonyls. The calculated results afford an understanding of the mechanism of previously reported photochemical alkane carbonylation systems utilizing d(8)-ML5 metal carbonyls as cocatalysts. In particular, it is strongly indicated that such systems operate via direct attack by an alkyl radical at a CO ligand, a reaction that has not previously been proposed.

Two iron-containing tungstogermanates: [K(H2O)(beta-Fe2GeW10O37(OH))(gamma-GeW10O36)]12- and [{beta-Fe2GeW10O37(OH)2}2]12-.

Interaction of the dilacunary polyanion precursor [gamma-GeW(10)O(36)](8-) with Fe(3+) ions in aqueous buffer medium (pH 4.8) results in the formation of two dimeric tungstogermanates depending on the reactant ratios. When using an Fe3+ to [gamma-GeW(10)O(36)](8-) ratio of 1:1, the asymmetric anion [K(H(2)O)(beta-Fe(2)GeW(10)O(37)(OH))(gamma-GeW(10)O(36))](12-) (1) is formed, whereas [{beta-Fe(2)GeW(10)O(37)(OH)2}2]12- (2) is formed when using a ratio of 2:1. Single-crystal X-ray analyses were carried out on Cs(3)K(9)[K(H(2)O)(beta-Fe(2)GeW(10)O(37)(OH))(gamma-GeW(10)O(36))].19H(2)O (CsK-1), which crystallizes in the triclinic system, space group P1, a = 11.4547(2), b = 19.9181(5), c = 21.0781(6) A, alpha = 66.7977(12), beta = 89.1061(12), gamma = 84.4457(11) degrees, and Z = 2 and on Cs(7)K(4)Na[{beta-Fe(2)GeW(10)O(37)(OH)(2)}(2)].39H(2)O (CsKNa-2), which crystallizes in the monoclinic system, space group C2/m, a = 32.7569(13), b = 12.2631(5), c = 14.2895(5) A, beta = 104.135(2) degrees , and Z = 2. Polyanion 1 consists of (beta-Fe(2)GeW(10)O(37)) and (gamma-GeW(10)O(36)) units linked via two Fe-O-W bridges and a central potassium ion. Two equivalent FeO(6) octahedra complete the belt of the beta-Keggin unit and link to the (gamma-GeW(10)O(36)) fragment. On the other hand, 2 consists of two {beta-Fe(2)GeW(10)O(37)(OH)(2)} units with four bridging hydroxo groups linking the four Fe(3+) ions, forming an eight-membered ring. The magnetic properties of CsK-1 and CsKNa-2 have been studied by magnetic susceptibility and magnetization measurements and fitted according to an isotropic exchange model. Both polyanions 1 and 2 exhibit diamagnetic ground states with a small amount of paramagnetic impurity. Electrochemistry studies on 1 and 2 were carried out in a pH 5 acetate medium. The two polyanions have in common the simultaneous reduction of all of their Fe(3+) centers. This observation suggests the existence of identical or almost-identical influences on these centers and their equivalence, especially in the reduced state. Controlled potential coulometry results indicate the presence of two Fe(3+) centers in 1 and four in 2. The splitting of the tungsten wave of 1 compared to the single tungsten wave of 2 is attributed to a difference in acid-base properties of the polyanions. Voltammetric peak-potential shifts as a function of pH were studied in the case of 2.

Organoruthenium derivative of the cyclic [H7P8W48O184]33- anion: [{K(H2O)}3{Ru(p-cymene)(H2O)}4P8W49O186(H2O)2]27-.

Reaction of [Ru(p-cymene)Cl2]2 with [H7P8W48O184]33- (P8W48) in aqueous acidic medium results in the organometallic derivative [{K(H2O)}3{Ru(p-cymene)(H2O)}4P8W49O186(H2O)2]27- (1); in addition to the four {Ru(p-cymene)(H2O)} units, an unusual WO6 group with four equatorial, terminal ligands is also grafted to the crown-shaped P8W48 precursor.

Dilacunary decatungstates functionalized by organometallic ruthenium(II), [{Ru(C6H6)(H2O)}{Ru(C6H6)}(gamma-XW10O36)]4- (X = Si, Ge).

The benzene-Ru(II)-supported dilacunary decatungstosilicate [{Ru(C6H6)(H2O)}{Ru(C6H6)}(gamma-SiW10O36)]4- and the isostructural decatungstogermanate [{Ru(C6H6)(H2O)}{Ru(C6H6)}(gamma-GeW10O36)]4- have been synthesized and characterized by multinuclear solution NMR, IR, elemental analysis, and electrochemistry. Single-crystal X-ray analysis was carried out on K4[{Ru(C6H6)(H2O)}{Ru(C6H6)}(gamma-SiW10O36)].9H2O (K-1), which crystallizes in the orthorhombic system, space group Pmn2(1), with a = 13.6702(3) A, b = 16.2419(4) A, c = 12.1397(2) A, and Z = 2, and on K4[{Ru(C6H6)(H2O)}{Ru(C6H6)}(gamma-GeW10O36)].7H2O (K-2), which also crystallizes in the orthorhombic system, space group Pmn2(1), with a = 13.6684(12) A, b = 16.297(2) A, c = 12.1607(13) A, and Z = 2. Polyanions 1 and 2 consist of a Ru(C6H6)(H2O) group and a Ru(C6H6) group linked to a dilacunary (gamma-XW10O36) Keggin fragment resulting in an assembly with idealized Cs symmetry. The Ru(C6H6)(H2O) group is bound at the lacunary polyanion site via two Ru-O(W) bonds, whereas the Ru(C6H6) group is bound on the side via three Ru-O(W) bonds. Polyanions 1 and 2 were synthesized in aqueous acidic medium at pH 2.5 by the reaction of [Ru(C6H6)Cl2]2 with [gamma-SiW10O36]8- and [gamma-GeW10O36]8-, respectively. The formal potentials are roughly the same for the first W waves of 1 and 2. However, important differences appear for the second W waves. These observations indicate different acid-base properties for the reduced forms of 1 and 2. Three oxidation processes were detected: the oxidation of the Ru center is followed first by irreversible electrocatalytic processes of the Ru-benzene moiety and then of the electrolyte. Comparison of this behavior with that of the precursor reagent, [Ru(C6H6)Cl2]2, was useful to understand the main oxidation processes. A ligand substitution reaction was observed upon addition of dimethyl sulfoxide (dmso) to 1, 2, or [Ru(C6H6)Cl2]2. This reaction facilitates substantially the oxidation of the Ru center. The dmso was oxidized with large electrocatalytic currents more efficiently in the presence of 1 and 2 than with [Ru(C6H6)Cl2]2.

Synthesis and structure of dilacunary decatungstogermanate, [gamma-GeW10O36]8-.

The dilacunary decatungstogermanate [gamma-GeW10O36]8- (1) has been synthesized and structurally characterized in solution and in the solid state. Reaction of germanium dioxide with sodium tungstate in aqueous acidic medium results in the formation of [beta2-GeW11O39]8- (2), which is then used as a precursor for the synthesis of 1. The (183)W spectrum of 2 shows the expected 11 peaks of equal intensity, whereas that of 1 exhibits the expected three peaks with relative intensities 2:2:1. Polyanion 1 represents a novel lacunary polyoxometalate, giving rise to a multitude of derivatives by reaction with transition metals, lanthanides, and other electrophiles.