Oxygen binding of water-soluble cobalt porphyrins in aqueous solution

Water-soluble cobalt porphyrin 1Co and imidazole ligand 2 were synthesized. 1Co binds dioxygen in the presence of imidazole ligand 2 in aqueous solution. The formation of the oxygen adduct 2-1Co(O(2)) was studied using UV-vis and EPR spectroscopy. The impact of pH on the kinetic stability of the oxygen adduct was examined.     

Catalytic Activation of H(2) and C-H Bonds by Electron-Deficient Ruthenium(II) Porphyrins

The Ru(2) and RuNi derivatives of 1,8-bis(10,15,20-trimesityl-5-porphyrinato)anthracene-a recently reported cofacial diporphyrin ligand comprising two hindered porphyrins spanned by an anthracene bridge-have been synthesized. Both Ru(2)(DPAHM) and RuNi(DPAHM) are extremely reactive species that apparently contain 14-electron Ru(II) centers and, as is the case for their monoporphyrin analog, (5,10,15,20-tetramesitylporphyrinato)ruthenium [Ru(TMP)], must be rigorously protected from oxygen, nitrogen, and other ligating agents. In addition, these electron-deficient Ru(II) porphyrins all appear to bind aromatic solvents such as benzene and toluene, the weakest ligating solvents in which these Ru(II) porphyrins have been found soluble. Ru(TMP) and its metallodiporphyrin analogs, Ru(2)(DPAHM) and RuNi(DPAHM), catalyze H(2)/D(2) exchange in benzene solution and as solids. When adsorbed on a particularly nonpolar carbon support, these Ru(II) porphyrins all manifest significant activity with respect to catalytic H(2)/D(2) exchange [approximately 40 turnovers s(-)(1), when normalized for Ru(II) content]. In addition, these molecules slowly catalyze the exchange of H(2) into deuterated aromatic hydrocarbons and, in the absence of solvent, the exchange of D(2) into CH(4). Kinetic studies of H(2)/D(2) exchange catalyzed by these Ru(II) porphyrins on carbon supports indicate that exchange is likely to be effected by one face of a single Ru(TMP) moiety. The activity of each supported catalyst was suppressed by the presence of ligands, either exogenous (CO irreversibly and N(2) reversibly) or from polar functionalities on the surface of the supporting matrix.     

Synthesis and characterization of Rh(III) corroles: unusual reactivity patterns observed during metalation reactions

A new approach to the synthesis of Rh(III) corrole complexes is developed and an unusual activation of C-C and C-N bonds is disclosed.     

Hybrid bilayer membrane: a platform to study the role of proton flux on the efficiency of oxygen reduction by a molecular electrocatalyst

In this report, we present a novel platform to study proton-coupled electron transfer (PCET) by controlling the proton flux using an electrode-supported hybrid bilayer membrane (HBM). Oxygen reduction by an iron porphyrin was used as a model PCET reaction. The proton flux was controlled by incorporating an aliphatic proton carrier, decanoic acid, into the lipid layer of the HBM. Using this system, we observed a different catalytic behavior than obtained by simply changing the pH of the solution in the absence of an HBM.     

Ferrocene embedded in an electrode-supported hybrid lipid bilayer membrane: a model system for electrocatalysis in a biomimetic environment

An electrode-supported system in which ferrocene molecules are embedded in a hybrid bilayer membrane (HBM) has been prepared and characterized. The redox properties of the ferrocene molecules were studied by varying the lipid and alkanethiol building blocks of the HBM. The midpoint potential and electron transfer rate of the embedded ferrocene were found to be dependent on the hydrophobic nature of the electrolyte and the distance at which the ferrocene was positioned in the HBM relative to the electrode and the solution. Additionally, the ability of the lipid-embedded ferrocenium ions to oxidize solution phase ascorbic acid was evaluated and found to be dependent on the nature of the counterion.     

Mixed azide-terminated monolayers: a platform for modifying electrode surfaces

We have prepared and characterized mixed self-assembled monolayers (SAM) on gold electrodes from azido alkane thiols and various omega-functionalized alkane thiols. In the presence of copper(I) catalysts, these azide-modified surfaces are shown to react rapidly and quantitatively with terminal acetylenes forming 1,2,3-triazoles, via "click" chemistry. The initial azide substituents can be identified and monitored using both grazing-angle infrared (IR) and X-ray photoelectron spectrosopies. Acetylenes possessing redox-active ferrocene substituents react with the azide-terminated mixed SAMs and electrochemical measurements of the ferrocene-modified SAM electrodes have been used to quantify the redox centers attached to these platforms. Time-resolved electrochemical measurements have enabled us to follow the formation of these ferrocene centers and thus to measure the rate of the surface "click" reaction. Under optimal conditions this well-behaved second-order reaction takes place with a rate constant of 1 x 10(3) M(-)(1) s(-)(1). Typical reaction times of several minutes were realized using micromolar concentrations of acetylene. These techniques have been used to construct well-characterized, covalently modified monolayers that can be employed as functional electrode surfaces.     

Synthesis and characterization of trans-[Os(en)2py(H)]2+ and related studies

trans-[Os(en)(2)pyH](Otf)(2), 2, is recovered from an acidic solution of trans-[Os(en)(2)py(H(2))](OTf)(2), 1, which has been subjected to one electron oxidation. The structures of both 1 and 2 have been determined by single crystal X-ray analysis. In cyclic voltammetry, 2 shows a one electron oxidation wave at 0.95 V and a one electron reduction wave at -1.2 V, neither accompanied by a signal for the reverse process. Reduction of 2 by Zn/Hg in methanol solution leads to quantitative formation of [Os(en)(2)(py)H(2))](2+), predominantly in the trans-form. In aqueous solution, species 2 reacts rapidly with N-methylacridium ion, [MAH](+), by hydride transfer. One electron chemical oxidation of 2 to the corresponding Os(IV) is slower than that of 1 to 2 owing to the increase in coordination number when Os(IV) is produced. Treatment of 1, or the cis-form, 1', in DMSO by sodium t-butoxide produces mainly the corresponding isomers of the monohydrides of Os(II), that derived from 1' is deep red in color while the trans-monohydride is colorless. Both react with [MAH](+) to form [MAH](2), and both disappear rapidly in acetone or acetonitrile, presumably by reducing the solvents. Reaction of trans-[Os(NH(3))(4)(H(2))H(2)O](BPh(4))(2), 4, in acetone-d(6) as solvent with either CH(3)CHO or styrene leads to hydrogenation of the substrate. Reactions which compete with trans-[Os(en)(2)(eta(2)-H(2))(CF(3)SO)(3)]CF(3)SO(3) release of substrate from the trans-complex before isomerization to the cis-form, required for hydrogenation to occur, result in the trans-derivative of the added solute. When H(2)C=CH-CH(2)-SCH(3) is the substrate, binding takes place at sulfur. Complete conversion to the cis-substrate isomer is observed, without hydrogenation occurring even though contact between dihydrogen and the double bond is possible.     

Radical autoxidation and autogenous O2 evolution in manganese-porphyrin catalyzed alkane oxidations with chlorite

A manganese porphyrin catalyst employing chlorite (ClO(2)(-)) as a "shunt" oxidant displays remarkable activity in alkane oxidation, oxidizing cyclohexane to cyclohexanol and cyclohexanone with >800 turnover numbers. The ketone is apparently formed without the intermediacy of alcohol and accounts for an unusually large fraction of the product ( approximately 40%). Radical scavenging experiments indicate that the alkane oxidation mechanism involves both carbon-centered and oxygen-centered radicals. The carbon-radical trap CBrCl(3) completely suppresses cyclohexanone formation and reduces cyclohexanol turnovers, while the oxygen-radical trap Ph(2)NH inhibits all oxidation until it is consumed. These observations are indicative of an autoxidation mechanism, a scenario further supported by TEMPO inhibition and (18)O(2) incorporation into products. However, similar cyclohexane oxidation activity occurs when air is excluded. This is explained by mass spectrometric and volumetric measurements showing catalyst-dependent O(2) evolution from the reaction mixture. The catalytic disproportionation of ClO(2)(-) into Cl(-) and O(2) provides sufficient O(2) to support an autoxidation mechanism. A two-path oxidation scheme is proposed to explain all of the experimental observations. The first pathway involves manganese-porphyrin catalyzed decomposition of ClO(2)(-) into both O(2) and an unidentified radical initiator, leading to classical autoxidation chemistry providing equal amounts of cyclohexanol and cyclohexanone. The second pathway is a "rebound" oxygenation involving a high-valent manganese-oxo intermediate, accounting for the excess of alcohol over ketone. This system highlights the importance of mechanistic studies in catalytic oxidations with highly reactive oxidants, and it is unusual in its ability to sustain autoxidation even under apparent exclusion of O(2).     

Synthesis and structural comparison of a series of divalent Ln(Tp(R,R)')2 (Ln = Sm, Eu, Yb) and trivalent Sm(Tp(Me2))2X (X = F, Cl, I, BPh4) complexes

Reaction of LnI2 (Ln = Sm, Yb) with two equivalents of NaTp(Me2) or reduction of Eu(Tp(Me2))2OTf gives good yields of the highly insoluble homoleptic Ln(II) complexes, Ln(Tp(Me2))2 (Ln = Sm (1a), Yb (2a), Eu (3a)). Use of the additionally 4-ethyl substituted Tp(Me2,4Et) ligand produces the analogous, but soluble Ln(Tp(Me2,4Et))2 (1-3b) complexes. Soluble compounds are also obtained with the Tp(Ph) and Tp(Tn) ligands (Tn = thienyl), Ln(Tp(Ph))2 (Ln = Sm, 1c; Yb, 2c) and Ln(Tp(Tn))2 (Ln = Sm, 1d; Yb, 2d). To provide benchmark parameters for structural comparison the series of Sm(Tp(Me2))2X complexes (X = F, 1e; Cl, 1f; Br, 1g; I, 1h; BPh4, 1j) were prepared either via oxidation of the Sm(Tp(Me2))2 or salt metathesis from SmX3 (X = Cl, Br, I). The solid-state structures of 1-3a, 1b, 1-2c and 1e, 1f, 1h, and 1j were determined by single-crystal X-ray diffraction. The homoleptic bis-Tp complexes are all six-coordinate with trigonal antiprismatic geometries, planes of the kappa(3)-Tp ligands are parallel to one another. In the series of Sm(Tp(Me2))2X complexes the structure changes from seven-coordinate molecular compounds, with intact Sm-X bonds, for X = F, Cl, to six-coordinate ionic structures [Sm(Tp(Me2))2]X (X = I, BPh4), suitable crystals of the bromide compound could not be obtained. The dependence of the structures on the size of X is understandable in terms of the interplay between the size of the cleft that the [Sm(Tp(Me2))2](+) fragment can make available and the donor ability of the anionic group toward the hard Sm(III) center.