Reactivity of an adsorbed Ru(VI)-oxo complex: oxidation of benzyl alcohol.

The phosphonated ruthenium complex, [Ru(tpy-PO(3)H(2))(OH(2))(3)](2+) (1) (tpy-PO(3)H(2) = 4'-phosphonato-2,2':6',2' '-terpyridine), was synthesized and attached to glass|ITO or glass|ITO|TiO(2) electrodes. After attachment to the metal oxide surface through the phosphonate linkage, 1 can be oxidized (either chemically or electrochemically) to the reactive Ru(VI)-dioxo complex, glass|ITO|[((HO)(2)OP)tpy)RuVI(O)(2)(OH(2))](2+), which remains attached to the surface. The attached Ru(VI) complex reacts with benzyl alcohol through mechanisms similar to those proposed for the solution analog. More specifically, Ru(VI) is reduced in a stepwise fashion to Ru(IV) and then finally to Ru(II). The reduction of Ru(VI) is accompanied by a rate-limiting insertion to the C-H bond of benzyl alcohol, followed by solvolysis of the aldehyde hydrate. In addition, the surface-bound Ru(VI) acts as an electrooxidation catalyst which carries out approximately 130 (2e(-)) turnovers before deactivation.

A test of the transition-metal nanocluster formation and stabilization ability of the most common polymeric stabilizer, poly(vinylpyrrolidone), as well as four other polymeric protectants.

Following an introduction to the nanocluster stabilization literature and DLVO (Derjaugin-Landau-Verwey-Overbeek) theory of colloidal stability, the most common steric stabilizer of transition-metal nanoclusters, poly(vinylpyrrolidone) (PVP), has been examined for its efficacy in the formation, stabilization, and subsequent catalytic activity of prototype, test case Ir(0)n nanoclusters. First, the five criteria established previously for ranking nanocluster protectants for their nanocluster formation and stabilization ability were evaluated for 1 monomer equiv of 10000 average molecular weight (MWav) PVP in the absence, and then presence, of the traditionally weakly coordinating anion BF4- as well as the absence and presence of the strongly coordinating, superior anionic stabilizer P2W15Nb3O62(9-), all in propylene carbonate solvent. It is found that neither 1 equiv of BF4- in propylene carbonate nor 1 monomer equiv of (undried) PVP alone allows for isolable and redissolvable nanoclusters without bulk Ir(0)n metal formation. Careful predrying of the PVP, and by implication other polymers, is shown to be necessary for the formation and stabilization of the nanoclusters. Next, 40 monomer equiv of 10000 MWav PVP and 1 equiv of BF4- in propylene carbonate are shown to allow isolable, redissolvable nanoclusters. Control experiments reveal little difference on nanocluster stabilization by 3500 or 55000 (i.e., vs 10,000) MWav PVP, but yield interesting effects on nanocluster nucleation by the 3500 MWav PVP, as well as by the polymer poly(bis(ethoxy)phosphazene) (PBEP). Four other key polymers reported in the literature to be nanocluster stabilizers are tested by the five criteria method for their efficacy in the formation and stabilization of Ir0n nanoclusters (now in acetone due to the polymers' solubility) and in comparison to each other, specifically, poly(methyl methacrylate) (PMMA), poly(styrene) (PS), poly(methylhydrosilane) (PMHS), and PBEP. Only 40 monomer equiv dried PMMA allows isolable and redissolvable nanoclusters in acetone. Control/reference point experiments show that the electrostatic stabilizer P2W15Nb3O62(9-) is superior to each of the five polymeric stabilizers studied herein in both acetone and propylene carbonate, at least for the test case of Ir(0)n nanoclusters. Further controls show that 40 monomer equiv of PVP added to P2W15Nb3O(62)9--stabilized nanoclusters has no discernible effect on the five criteria other than to reduce by approximately 50% the nanocluster catalytic activity and total catalytic lifetime for cyclohexene hydrogenation. The main finding of this work is that DLVO theory as applied to nanocluster stabilization is fully supported; that is, surface-bound anions in high dielectric constant solvents provide superior stabilization. The importance of even traditionally weakly coordinating anions such as BF4- in nanocluster stabilization is a second, important finding of this work. The fact that HPO4(2-) has been shown to be a simple, cheap, commercially available, thermally robust, and 31P-NMR-handle-containing analogue of the more esoteric P2W15Nb3O62(9-) stabilizer is also discussed in the 14 total Conclusions from this first study ranking polymeric stabilizers of modern transition-metal nanoclusters.

Synthesis and characterization of oligoproline-based molecular assemblies for light harvesting.

Helical oligoproline arrays provide a structurally well-defined environment for building photochemical energy conversion assemblies. The use of solid-phase peptide synthesis (SPPS) to prepare four such arrays, consisting of 16, 17, 18, and 19 amino acid residues, is described here. Each array contains the chromophore [Rub'(2)m](PF(6))(2) (b' = 4,4'-diethylamidocarbonyl-2,2'-bipyridine; m = 4-methyl-2,2'-dipyridine-4'-carboxylic acid) and the electron transfer donor PTZ (phenothiazine). The arrays differ systematically in the distance between the redox-active metal complex and PTZ sites. They have been used in photophysical studies to provide insight into the distance dependence of electron transfer. (J. Am. Chem. Soc. 2004, 126, 14506-14514). This work describes the synthesis, purification, and characterization of the oligoproline arrays, including a general procedure for the synthesis of related arrays.

Photoelectrochemistry on Ru(II)-2,2'-bipyridine-phosphonate-derivatized TiO2 with the I3-/I- and quinone/hydroquinone relays. Design of photoelectrochemical synthesis cells.

Photocurrent measurements have been made on nanocrystalline TiO2 surfaces derivatized by adsorption of a catalyst precursor, [Ru(tpy)(bpy(PO3H2)2)(OH2)]2+, or chromophore, [Ru(bpy)2 (bpy(PO3H2)2)]2+ (tpy is 2,2':6',2' '-terpyridine, bpy is 2,2'-bipyridine, and bpy(PO3H2)2 is 2,2'-bipyridyl-4,4'-diphosphonic acid), and on surfaces containing both complexes. This is an extension of earlier work on an adsorbed assembly containing both catalyst and chromophore. The experiments were carried out with the I3-/I- or quinone/hydroquinone (Q/H2Q) relays in propylene carbonate, propylene carbonate-water mixtures, and acetonitrile-water mixtures. Electrochemical measurements show that oxidation of surface-bound Ru(III)-OH2(3+) to Ru(IV)=O(2+) is catalyzed by the bpy complex. Addition of aqueous 0.1 M HClO4 greatly decreases photocurrent efficiencies for adsorbed [Ru(tpy)(bpy(PO3H2)2)(OH2)]2+ with the I3-/I- relay, but efficiencies are enhanced for the Q/H2Q relay in both propylene carbonate-HClO4 and acetonitrile-HClO4 mixtures. The dependence of the incident photon-to-current efficiency (IPCE) on added H2Q in 95% propylene carbonate and 5% 0.1 M HClO4 is complex and can be interpreted as changing from rate-limiting diffusion to the film at low H2Q to rate-limiting diffusion within the film at high H2Q. There is no evidence for photoelectrochemical cooperativity on mixed surfaces containing both complexes with the IPCE response reflecting the relative surface compositions of the two complexes. These results provide insight into the possible design of photoelectrochemical synthesis cells for the oxidation of organic substrates.

The kinetics and mechanism of the ferrate(VI) oxidation of hydroxylamines.

Aqueous solutions of potassium ferrate(VI) cleanly and rapidly oxidize hydroxylamine to nitrous oxide, N-methylhydroxylamine to nitrosomethane, N-phenylhydroxylamine to nitrosobenzene, and O-methylhydroxylamine to methanol and nitrogen. The kinetics show first-order behavior with respect to each reactant and a two term component representing acid dependent and independent pathways. A general mechanism involving intermediate formation coupled with a two-electron oxidation is proposed.

The lacunary polyoxoanion synthon alpha-P(2)W(15)O(56)(12-): an investigation of the key variables in its synthesis plus multiple control reactions leading to a reliable synthesis.

A reliable way to determine the purity of the kinetically precipitated, noncrystalline lacunary polyoxoanion alpha-P(2)W(15)O(56)(12-) has been developed, namely, the conversion of alpha-P(2)W(15)O(56)(12-) into the tri-Nb(5+)- and V(5+)-containing polyoxoanions P(2)W(15)Nb(3)O(62)(9-) and P(2)W(15)V(3)O(62)(9-), respectively, followed by quantitative analysis of their purity by (31)P-NMR prior to recrystallization. With this previously unappreciated, straightforward alpha-P(2)W(15)O(56)(12-) purity-assessment methodology in hand, the five reported literature syntheses of alpha-P(2)W(15)O(56)(12-) are investigated with an emphasis on understanding the effects of the five differing variables within these syntheses (the amount of Na(2)CO(3) base, the rate of addition of the base, the reaction temperature, the reaction scale, and the product drying method). Two methods of Nb(5+) addition (Nb(6)O(19)(8-) and NbCl(5)) to yield P(2)W(15)Nb(3)O(62)(9-) are also evaluated, as is the issue of whether any purification is provided by the normally optimum strategy of first preparing a water-soluble salt and its crystallization from water (here the (CH(3))(4)N(+) salt of the Nb-O-Nb bridged anhydride, P(4)W(30)Nb(6)O(123)(16-)), followed by its conversion to the organic-solvent soluble, but noncrystalline, (n-C(4)H(9))(4)N(+) salt, [(n-C(4)H(9))(4)N](9)[P(2)W(15)Nb(3)O(62)]. The results yield five previously unavailable and unequivocal insights: (1) Only the amount of added Na(2)CO(3) base affects the purity or yield of the desired alpha-P(2)W(15)O(56)(12-); the amount of added base is key, however. (2) Contant's 1990 Inorganic Syntheses procedure provides the highest-purity alpha-P(2)W(15)O(56)(12-) presently available. (3) All prior syntheses calling for the addition of base to P(2)W(18)O(62)(6-) until pH 9 must be abandoned. (4) The purity of even Contant's alpha-P(2)W(15)O(56)(12-) is only 90%. (5) An identifiable impurity is the 16 tungsten polyoxoanion, alpha-P(2)W(16)()O(59)(12-). Also identified and summarized are multiple compounding errors in the observation of, reporting on, and thinking about the synthesis of alpha-P(2)W(15)O(56)(12-) historically, errors which delayed the most reliable synthesis of alpha-P(2)W(15)O(56)(12-) from being identified for 18 years (from the 1983 discovery of alpha-P(2)W(15)O(56)(12-)). However, these errors yield valuable take-home lessons for anyone interested in working in this demanding area of inorganic synthetic chemistry, where direct structural methods for identifying the products and their purity, such as the lacunary polyoxoanion synthon alpha-P(2)W(15)O(56)(12-), sometimes simply do not exist.

Nanoclusters in catalysis: a comparison of CS(2) catalyst poisoning of polyoxoanion- and tetrabutylammonium-stabilized 40 +/- 6 A Rh(0) nanoclusters to 5 Rh/Al(2)O(3), including an analysis of the literature related to the CS(2) to metal stoichiometry issue.

It is crucial in metal particle catalysis to know the true number of catalytically active surface sites; without this knowledge it is impossible (i) to know the true turnover frequency (TOF, i.e., the moles of product/(moles of active metal atoms x time)); (ii) to know for certain whether a (quantitatively) better catalyst has been made-on a per-active-metal-atom basis; (iii) to know the amount of active sites remaining in a deactivated catalyst; and (iv) to know how many active sites have been regenerated in a reactivated catalyst. For this reason, herein we report the first quantitative, more complete and fundamental study of nanocluster catalyst poisoning using the preferred CS(2) method with polyoxoanion- and tetrabutylammonium-stabilized Rh(0) nanoclusters; 5% Rh/Al(2)O(3) is also examined as a valuable comparison point. Both catalysts are examined under essentially identical conditions and while catalyzing a prototype reaction, cyclohexene hydrogenation. A number of control studies are also reported to be sure that the kinetic method used to follow the CS(2) poisoned hydrogenation reaction is reliable, to test for H(2) gas-to-solution mass-transfer limitations, to test for reversibility in the CS(2) poisoning, and to test for loss of the volatile CS(2). The results allow 10 previously unavailable insights and conclusions, including the first quantitative comparison of the active-site corrected TOF for a nanocluster catalyst (in this case Rh(0) nanoclusters) to its supported heterogeneous counterpart (the 5% Rh(0) on Al(2)O(3)). The results show that the nanocluster surface Rh(0) is between 2.3 and 23 times more active on a per-active-metal-atom basis. Overall, the results introduce to the transition-metal nanocluster area the catalyst poisoning methodology necessary for the determination of the number of active metal sites. The important literature of CS(2) catalyst poisoning studies is also cited and discussed with a focus on the previously neglected issue of the exact poison/metal stoichiometry ratio. Significantly, the single metal crystal plus CS(2) literature provides evidence that the CS(2)/metal ratio probably lies between 1/1.5 and 1/10 in most cases. The data presented herein suggest that the CS(2)/Rh ratio for the Rh(0) nanoclusters is very likely within this range and for certain is <1/17.