One-electron Oxidation Processes Research Articles

Metallocene-catalyzed synthesis of polyethylenes with side-chain triarylamines: Effects of catalyst structure and triarylamine functionality

The copolymerization of ethylene with 8-triarylamine (TAA) substituted 1-octene monomers (TAA = triphenylamine (M1), N,N-diphenyl-m-tolylamine (M2), N,N-diphenyl-1-naphthylamine (M3)) using various types of group 4 single-site catalytic systems (Cp2ZrCl2 (C1), rac-EBIZrCl2 (C2), rac-SBIZrCl2 (C3), i-PrCpFluZrCl2 (C4), Me2Si(η5-C5Me4)(η1-N-tBu)TiCl2 (C5)) was investigated to prepare functionalized polyethylene with side-chain TAA groups. The metallocene/methylaluminoxane (MAO) catalytic systems (C1–C4) efficiently lead to the production of high-molecular-weight poly(ethylene-co-M1). While the C4/MAO catalytic system shows the highest comonomer response, the C5/MAO system exhibits the poor compatibility with the M1 comonomer. Copolymerization results of ethylene with M1–M3 using C4/MAO indicate that M1–M3 are well tolerated by both the cationic active species of C4 and MAO cocatalyst, giving rise to the copolymers with high levels of activity and molecular weight. Inspection of the aliphatic region of the 13C NMR spectra of the copolymers (P1–P3) having ca. 11 mol% of M1–M3, respectively, reveals the presence of isolated comonomer units with prevailing [EEMEE] monomer sequences in the polymer chain. UV–vis absorption and PL spectra exhibit an apparent low-energy band broadening for P1 and P2 indicative of intrachain aggregate formation. Whereas P2 and P3 undergo completely reversible one-electron oxidation process, P1 shows relatively poor oxidational stability.

Modifiying glassy carbon electrode with ferrocene-bridged polysilsesquioxanes

Ferrocene-bridged polysilsesquioxanes film electrodes were prepared via depositing the sols formed by hydrolysis of 1,1′-bis[(2-triethoxylsilyl)ethyl]ferrocene (BTEF) or co-hydrolysis of poly(vinylalcohol) (PVA) with BTEF or tetraethoxysilane (TEOS) with BTEF onto glassy carbon electrode (GCE) surface. The electrochemical behavior of the modified electrodes were characterized by cyclic voltammogram (CV) in aqueous solution. The BTEF film, BTEF/PVA film and BTEF/TEOS film all exhibit a redox wave at E0’ are 0.504, 0.326, 0.318 V, with the peak potential separation (ΔE) are 0.132, 0.042, 0.028 V, and the value of ipa/ipc are 1.8097, 1.007, 1.064 (vs. SCE), respectively. This suggests that BTEF/PVA film and BTEF/TEOS film have a good reversible redox behavior and the redox peak is corresponded to a one-electron reduction and oxidation process. After successive 50 time’s cyclic voltammetric, there is no peak potential shift, and the peak current only decreased 5.58, 4.95%, respectively. BTEF/PVA film has better hydrophilicity and shows a more perfect electrocatalytic activity in the oxidation of H2A than that of the BTEF/TEOS film. The catalytic peak current has a linear relationship with the concentration of H2A in the range of 1.0 × 10−5~1.0 × 10−3 M.

Symmetrical linear Co 36+ chains cocooned by two polypyridylamide ligands: How do they compare to open chains?

Two extended metal atom chain (EMAC) compounds having a symmetrical Co 3 6+ metal chain encapsulated by two N, N′-bis[(6′-pyrid-2″-yl)aminopyrid-2′yl]-bismethyl-2,6-diaminopyridinate (mpeptea) ligands have been prepared in good yield, and they have been structurally characterized by X-ray crystallography, magnetic and electrochemical measurements and spectroscopic techniques. For the EMAC [Co 3(mpeptea) 2]Cl 2 two solvates have been crystallized. Anion exchange has also allowed isolation of [Co 3(mpeptea) 2](BPh 4) 2. In these three species the Co 3 6+ units are cocooned within two polypyridine ligands having nine nitrogen atoms although only seven of these coordinate to the metal centers. The cations [Co 3(mpeptea) 2] 2+ are similar and have Co ··· Co separations of ca. 2.3 Å at 213 K. These distances are consistent with partial bond formation between Co atoms. Electrochemical measurements show a unique one-electron oxidation process that differs from that in open chain species which show two reversible oxidation processes. At 300 K, the χT value is 7.32 emu K mol −1 but this value drops to 1.47 emu K mol −1 as the temperature is lowered to 2 K. The X-band EPR spectra for Co 3(mpeptea) 2 2+ show g values of 2.3 at room temperature. The magnetic behavior is quite different from that in compounds with open Co 3 6+ units. A discussion is provided.

Electrochemical and in situ spectroelectrochemical investigations into the redox and aggregation behaviours of phthalocyanines bearing octyl 4-phenyloxyacetate moieties

Electrochemical and spectroelectrochemical properties of phthalocyanines (H2Pc, ZnPc, NiPc, CuPc, and CoPc) involving octyl 4-phenyloxyacetate moieties have been investigated by cyclic voltammetry and differential pulse voltammetry on Pt in dimethylsulfoxide – tetrabutylammonium perchlorate. These measurements showed that the complexes undergo subsequent one-electron reduction and oxidation processes. In situ UV–vis spectroelectrochemical measurements enabled us to identify the ligand- and metal-based redox processes, and evaluate the effect of aggregation phenomena on these processes. The cobalt complex showed both metal-based and ring-based one-electron redox processes, while the other complexes displayed only ring-based one-electron couples. It was observed that the redox processes of H2Pc, NiPc, and CuPc are coupled by aggregation phenomenon, whereas those of ZnPc and especially CoPc are not, probably owing to the difference in their axial coordinating properties.

Synthesis, Structure, and Electrochemistry of the Dicluster Molecular Pincer [Pt3(μ-PBut2)3(CO)2]2(μ-1′,1′′′-diethynylbiferrocene)

The CuI catalyzed dehydro-halogenation of 1',1'''-diethynylbiferrocene and {Pt(3)}Cl [{Pt(3)} = Pt(3)(mu-PBu(t)(2))(3)(CO)(2)] (1:2 molar ratio) in diethylamine gives in high yields the bicluster derivative [{Pt(3)}CC-(eta(5)-C(5)H(4))Fe(eta(5)-C(5)H(4))](2), 3, in which two platinum triangles are connected by a diethynylbiferrocene spacer. In the structure of 3, confirmed by a diffractometric study, the two {Pt(3)} fragments lie, perfectly eclipsed, on the same side of the biferrocenyl moiety; this folded structure is also preferred in solution, as suggested by NMR Diffusion Ordered Spectroscopy (DOSY) and 1D Rotating-frame Overhauser Enhancement (ROE) measurements. Compound 3 exhibits a rich redox behavior, with a crowded sequence of six one-electron oxidation processes, the electrode potentials of which have been evaluated by digital simulations. On the basis of a spectroelectrochemical study, the first two oxidations are assigned to the iron centers of the diferrocenyl unit and the subsequent four electrons are removed from the {Pt(3)} units.

Efficient Photoinduced Electron Transfer in a Porphyrin Tripod−Fullerene Supramolecular Complex via π−π Interactions in Nonpolar Media

A novel porphyrin tripod (TPZn(3)) was synthesized via "click chemistry". Three porphyrin moieties of TPZn(3) are geometrically close and linked by a flexible linker. The electron-transfer oxidation of TPZn(3) results in intramolecular pi-dimer formation between porphyrin moieties as indicated by electrochemical, vis-NIR, and ESR measurements. The cyclic voltammogram of TPZn(3) exhibited stepwise one-electron oxidation processes of three porphyrin moieties in the range from 0.58 to 0.73 V (vs SCE in CH(2)Cl(2)). When TPZn(3) was oxidized by tris(2,2'-bipyridyl)-ruthenium(III) ([Ru(bpy)(3)](3+)), the oxidized species (TPZn(3))(n+) (0 < n </= 3) exhibited a charge resonance band in the NIR region due to the pi-dimer formation between porphyrin moieties. A supramolecular electron donor-acceptor system was also constructed using TPZn(3). The flexible conformation of TPZn(3) makes it possible to capture a fullerene derivative containing a pyridine moiety (PyC(60)) inside the cavity by pi-pi interactions as well as the coordination bond between Zn(2+) and the pyridine moiety. The formation of a 1:1 supramolecular complex of TPZn(3) with PyC(60) (TPZn(3)-PyC(60)) was indicated in the UV-vis and (1)H NMR spectra in nonpolar solvents. The association constant of TPZn(3) with PyC(60) (1.1 x 10(5) M(-1) in toluene) is much larger as compared with those of the corresponding monomer (MPZn) and dimer porphyrin (DPZn(2)). The dynamics of photoinduced electron transfer from the singlet excited state of TPZn(3) to PyC(60) was examined by laser flash photolysis measurements. The efficient intracomplex photoinduced electron transfer in TPZn(3)-PyC(60) occurred in nonpolar solvents, resulting from the pi-pi interactions between the porphyrin and fullerene moieties, together with intramolecular pi-bond formation between the porphyrin radical cation and the neutral porphyrin in TPZn(3)(*+).

Octahedral Copper(II) and Tetrahedral Copper(I) Double-Strand Helicates: Chiral Self-Recognition and Redox Behavior

The racemic form of 5 ((RR)5 + (SS)5) gives dinuclear complexes of 2:2 stoichiometry both with Cu(II), acting as a bis-terdentate ligand, and with Cu(I), acting as a bis-bidentate ligand. Single crystal X-ray diffraction studies have shown that the Cu(II) complex exists as double-strand homochiral helicate molecules: P,P-[Cu(2)(II)((RR)5)(2)](4+) and M,M-[Cu(2)(II)((SS)5)(2)](4+); in which the two trans-1,2-cyclohexanediamine subunits have the same chirality for of the two strands. Each Cu(II) metal center is six-coordinated according to a cis-octahedral geometry and interacts with a NNO donor subunit of each strand. The Cu(I) complex, when crystallized from THF in the presence of (rac)5, gives a double-strand homochiral helicate complex and in the solid state forms a racemic mixture of the homochiral metal complexes M,M-[Cu(2)(I)((RR)5)(2)](2+) and P,P-[Cu(2)(I)((SS)5)(2)](2+). When crystallizing from a MeCN solution, Cu(I) and (rac)5 give rise to the heterochiral nonhelicate dimeric complex [Cu(2)(I)((RR)5)((SS)5)](2+), in which the two strands of the dimer have inverse configuration of the trans-1,2-cyclohexanediamine subunits and are assembled side-by-side. In both structural architectures, the Cu(I) centers are four-coordinated by two nitrogen atoms from each strand, according to a distorted tetrahedral geometry. In MeCN solution, the dinuclear Cu(II) complex disassembles to give the mononuclear species, which, on reduction at a platinum electrode in a cyclic voltammetry experiment, gives two Cu(I) mononuclear complexes that quickly assemble to give the dinuclear Cu(I) complex. This complex undergoes two consecutive one-electron oxidation processes, but the dinuclear Cu(II) species that forms decomposes in less than 1 s. On the contrary, the [Cu(2)(I)((rac)5)(2)](2+) complex is stable in MeCN solution and undergoes two one-electron oxidation processes to give a form of dinuclear Cu(II) complex that lasts in solution for more than 20 s.

Synthesis and electrochemistry of multiwalled carbon nanotube films directly attached on silica substrate

Vertically aligned multiwalled carbon nanotubes (MWCNT) on silica substrate were selectively produced by the procedure of chemical vapor deposition (CVD). For the synthesis of the MWCNT films, either acetonitrile (ACN) or benzene (BZ) was used as carbon sources while ferrocene (FeCp2) was adopted as catalyst. The packing organization of the aligned carbon nanotubes on the silica substrate, and thus the degree of disorder of the produced MWCNT films, was found to be different. Namely, the MWCNT2 film, produced upon decay of BZ, seems to be more disordered compared to MWCNT1, produced upon decomposition of ACN. In order to examine their prospective application as electrodes for the detection of electroactive compounds in organic solvent media, the techniques of cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS) were employed. FeCp2 was selected as the suitable standard electroactive substance for probing the fabricated MWCNT electrodes, in view of the fact that FeCp2 undergoes a fast one-electron oxidation process forming the ferrocenium cation (FeCp2+), which is rather stable during the time scale of the experiments. All electrochemical experiments were performed in ACN as solvent medium including n-tetrabutylammonium hexafluorophosphate as supporting electrolyte at room temperature. The extracted CV and EIS results were compared with those obtained using glassy carbon electrode. The findings demonstrate the successful detection of FeCp2 in ACN at both MWCNT films. However, among the films investigated, the electrode produced upon decay of BZ seems to be better capacitor, most probably due to its higher surface area as well as to its small film thickness. Evidently, the high degree of disorder, which has been observed for MWCNT2, plays an important role for the increase of its effective surface area and thus, its capacitance. It is, however, very interesting that the more disorder MWCNT2 film provides, the greater charge transfer resistance.

Electrochemical and optical properties of biphenyl bridged-dicarbazole oligomer films: Electropolymerization and electrochromism

4,4′-Di( N-carbazoyl)biphenyl monomer (CBP) was synthesized and coated onto ITO–glass surface by electrochemical oxidative polymerization. Its CV shows two distinct one-electron and stepwise oxidation processes occurred at 1.29 and 1.61 V. By using this property, the monomer was electrochemically polymerized separately at these oxidation states and thus, two different oligomer films were obtained afterwards. Their spectro-electrochemical and electrochromic properties were also investigated. Switching ability of the oligomers was evaluated by kinetic studies upon measuring the percent transmittance (% T) at their maximum contrast point, indicating that these oligomers were found to be suitable material for electrochromic devices.

One- and Two-Electron Reactivity of a Tantalum(V) Complex with a Redox-Active Tris(amido) Ligand

A new redox-active, tris(amido) ligand platform, bis(2-isopropylamino-4-methoxyphenylamine [NNN(cat)](3-), has been prepared and used in the preparation of tantalum(V) complexes. The ligand was prepared in its protonated form by a three-step procedure from commercially available 4-methoxy-2-nitroaniline and 1-iodo-4-methoxy-2-nitrobenzene. Direct reaction of [NNN(cat)]H(3) with TaCl(2)Me(3) afforded five-coordinate [NNN(cat)]TaCl(2) (1), which accepted the strong sigma-donor ligand (t)BuNC to form the six-coordinate adduct [NNN(cat)]TaCl(2)(CN(t)Bu) (2). Complex 1 is formally a d(0), Ta(V) complex; however, one- and two-electron reactivity is enabled at the metal center by the redox-activity of the ligand platform. Complex 1 was oxidized by one electron to afford the radical species [NNN(sq*)]TaCl(3) (3), which was characterized by solution EPR spectroscopy. Cyclic voltammetry studies of complex 3 showed clean one-electron oxidation and reduction processes at 0.148 and -0.324 V vs [Cp(2)Fe](+/0), indicating the accessibility of three oxidation states, [NNN(cat)](3-), [NNN(sq*)](2-), and [NNN(q)](-), for the metallated ligand. Complex 1 also can undergo two-electron reactions, as evidenced by the reaction with nitrene transfer reagents to form tantalum imido species. Thus 1 reacted with organic azides, RN(3) (R = Ph, p-C(6)H(4)Me, p-C(6)H(4)(t)Bu), to form [NNN(q)]TaCl(2)(NR) (4). Similarly, the tantalum diphenylmethylidenehydrazido complex, [NNN(q)]TaCl(2)(NNCPh(2)) (5), was formed by reaction of 1 with the diazoalkane, N(2)CPh(2).

Electrochemical investigation of Mn4O4-cubane water-oxidizing clusters

High valence states in manganese clusters are a key feature of the function of one of the most important catalysts found in nature, the water-oxidizing complex of photosystem II. We describe a detailed electrochemical investigation of two bio-inspired manganese-oxo complexes, [Mn(4)O(4)L(6)] (L = diphenylphosphinate (1) and bis(p-methoxyphenyl)phosphinate (2)), in solution, attached to an electrode surface and suspended within a Nafion film. These complexes contain a cubic [Mn(4)O(4)](6+) core stabilized by phosphinate ligands. They have previously been shown to be active and durable photocatalysts for the oxidation of water to dioxygen. A comparison of catalytic photocurrent generated by films deposited by two methods of electrode immobilization reveals that doping of the catalyst in Nafion results in higher photocurrent than was observed for a solid layer of cubane on an electrode surface. In dichloromethane solution, and under conditions of cyclic voltammetry, the one-electron oxidation processes 1/1(+) and 2/2(+) were found to be reversible and quasi-reversible, respectively. Some decomposition of 1(+) and 2(+) was detected on the longer timescale of bulk electrolysis. Both compounds also undergo a two-electron, chemically irreversible reduction in dichloromethane, with a mechanism that is dependent on scan rate and influenced by the presence of a proton donor. When immersed in aqueous electrolyte, the reduction process exhibits a limited level of chemical reversibility. These data provide insights into the catalytic operation of these molecules during photo-assisted electrolysis of water and highlight the importance of the strongly electron-donating ligand environment about the manganese ions in the ability of the cubanes to photocatalyze water oxidation at low overpotentials.

Synthesis, in situ spectroelectrochemistry and in situ electrocolorimetry of electrochromic octakis(chloroethylsulfanyl) phthalocyaninatomanganese(iii) chloride

In this study, the syntheses of octakis(hydroxyethylsulfanyl) phthalocyaninatomanganese(III) chloride and its chlorinated derivative, octakis(chloroethylsulfanyl) phthalocyaninatomanganese(III) chloride, and successive electrochemical investigations of the latter were reported. The voltammetric studies of the complex revealed that it exhibits three one-electron reduction processes and a one-electron oxidation process. In situ spectroelectrochemical studies were performed to decide the origin of the redox processes which are assigned to MnIIIPc2−/MnIIPc2−, MnIIPc2−/MnIPc2−, MnIPc2−/MnIPc3− and MnIIIPc2−/MnIIIPc1− couples, respectively. The presence of oxygen significantly affected the in situ spectroelectrochemical behavior of the complexes due to the formation of μ-oxo MnPc species. An in situ electrocolorimetric method, based on the 1931 CIE (Commission Internationale de l’Eclairage) system of colorimetry, was applied to investigate the color of the electrogenerated anionic and cationic forms of the complex, which shows solvatochromic properties of the complex in solution. The possible polyelectrochromic application on solid state was suggested due to the color changes from brown to greenish blue and from brown to light yellow of a MnPc-coated thin film on ITO.

Photoinduced Charge-Transfer Processes on MOF-5 Nanoparticles: Elucidating Differences between Metal-Organic Frameworks and Semiconductor Metal Oxides

Metal-organic frameworks (MOFs), which exhibit large surface area and porosity retention upon solvent removal, have attracted considerable attention due to their elegant topology and potential applications in separation, gas storage, nonlinear optics, and catalysis. We report herein comprehensive studies on the nature of luminescence transitions in MOF-5 nanoparticles, which are referred to as MOF-5_n, and the interfacial charge transfer from the photoexcited MOF-5_n to various organic compounds. The time-resolved diffuse reflectance (TDR) and fluorescence spectroscopies were combined in order to clarify the photoinduced one-electron oxidation processes of organic compounds on the MOF-5_n. First, to identify the nature of the luminescence transitions in MOF-5, the temperature dependences of the spectral characteristics were elucidated and compared with those of ZnO nanoparticles. The quenching of MOF-5 emission by several substrates (S), such as aromatic sulfides and amines, was then investigated using steady-state and time-resolved fluorescence spectroscopies. The one-electron oxidation reaction of S during the 355 nm laser flash photolysis of MOF-5_n in acetonitrile was directly examined using TDR spectroscopy, and it was revealed that MOF-5 has a much higher oxidation reaction efficiency than that of P-25 TiO2 powder, which is the most common photocatalyst. The experimental data were rationalized in terms of the Marcus theory on the electron transfer reactions. Moreover, the influence of adsorbed water on the reaction processes was examined because the MOF crystal morphology is affected by exposure to water during synthesis or after evacuation. Consequently, the present study provides an excellent opportunity to understand the difference in the photoinduced charge-transfer processes between MOFs and semiconductors.

Tuning of the [Cu3(μ-O)]4+/5+Redox Couple: Spectroscopic Evidence of Charge Delocalization in the Mixed-Valent [Cu3(μ-O)]5+Species

Trinuclear Cu (II)-complexes of formula [Cu (II) 3(mu 3-E)(mu-4-R-pz) 3X 3] (+/- n ), E = O and OH; R = H, Cl, Br, CH(O) and NO 2; X = Cl, NCS, CH 3COO, and py, have been synthesized and characterized and the effect of substitution of terminal ligands, as well as 4-R-groups, in the one-electron oxidation process has been investigated by cyclic voltammetry. In situ UV-vis-NIR spectroelectrochemical characterization of the mixed valence Cu 3 (7+)-complex [Cu 3(mu 3-O)(mu-pz) 3Cl 3] (-) revealed an intervalence charge transfer band at 9550 cm (-1) (epsilon = 2600 cm (-1) M (-1)), whose analysis identifies this species as a delocalized, Robin-Day class-III system, with an electronic coupling factor, H ab, of 4775 cm (-1).

Redox Properties of Ruthenium Nitrosyl Porphyrin Complexes with Different Axial Ligation: Structural, Spectroelectrochemical (IR, UV−Visible, and EPR), and Theoretical Studies

Experimental and computational results for different ruthenium nitrosyl porphyrin complexes [(Por)Ru(NO)(X)] ( n+ ) (where Por (2-) = tetraphenylporphyrin dianion (TPP (2 (-) )) or octaethylporphyrin dianion (OEP (2-)) and X = H 2O ( n = 1, 2, 3) or pyridine, 4-cyanopyridine, or 4- N,N-dimethylaminopyridine ( n = 1, 0)) are reported with respect to their electron-transfer behavior. The structure of [(TPP)Ru(NO)(H 2O)]BF 4 is established as an {MNO} species with an almost-linear RuNO arrangement at 178.1(3) degrees . The compound [(Por)Ru(NO)(H 2O)]BF 4 undergoes two reversible one-electron oxidation processes. Spectroelectrochemical measurements (IR, UV-vis-NIR, and EPR) indicate that the first oxidation occurs on the porphyrin ring, as evident from the appearance of diagnostic porphyrin radical-anion vibrational bands (1530 cm (-1) for OEP (*-) and 1290 cm (-1) for TPP (*-)), from the small shift of approximately 20 cm (-1) for nu NO and from the EPR signal at g iso approximately 2.00. The second oxidation, which was found to be electrochemically reversible for the OEP compound, shows a 55 cm (-1) shift in nu NO, suggesting a partially metal-centered process. The compounds [(Por)Ru(NO)(X)]BF 4, where X = pyridines, undergo a reversible one-electron reduction. The site of the reduction was determined by spectroelectrochemical studies to be NO-centered with a ca. -300 cm (-1) shift in nu NO. The EPR response of the NO (*) complexes was essentially unaffected by the variation in the substituted pyridines X. DFT calculations support the interpretation of the experimental results because the HOMO of [(TPP)Ru(NO)(X)] (+), where X = H 2O or pyridines, was calculated to be centered at the porphyrin pi system, whereas the LUMO of [(TPP)Ru(NO)(X)] (+) has about 50% pi*(NO) character. This confirms that the (first) oxidation of [(Por)Ru(NO)(H 2O)] (+) occurs on the porphyrin ring wheras the reduction of [(Por)Ru(NO)(X)] (+) is largely NO-centered with the metal remaining in the low-spin ruthenium(II) state throughout. The 4% pyridine contribution to the LUMO of [(TPP)Ru(NO)(py)] (+) is correlated with the stability of the reduced form as opposed to that of the aqua complex.

Molecular and Electronic Structures of One‐Electron Oxidized NiII–(Dithiosalicylidenediamine) Complexes: NiIII–Thiolate versus NiII–Thiyl Radical States

The dithiosalicylidenediamine Ni II complexes [Ni(L)] (R=tBu, R'=CH2C(CH3)2CH2 1, R'=C6H4 2; R=H, R'=CH2C(CH3)2CH2 3, R'=C6H4 4) have been prepared by transmetallation of the tetrahedral complexes [Zn(L)] (R=tBu, R'=CH2C(CH3)2CH2 7, R'=C6H4 8; R=H, R'=CH2C(CH3)2CH2 9, R'=C6H4 10) formed by condensation of 2,4-di-R-thiosalicylaldehyde with diamines H2N-R'-NH2 in the presence of Zn II salts. The diamagnetic mononuclear complexes [Ni(L)] show a distorted square-planar N2S2 coordination environment and have been characterized by 1H- and 13C NMR and UV/Vis spectroscopies and by single-crystal X-ray crystallography. Cyclic voltammetry and coulombic measurements have established that complexes 1 and 2, incorporating tBu functionalities on the thiophenolate ligands, undergo reversible one-electron oxidation processes, whereas the analogous redox processes for complexes 3 and 4 are not reversible. The one-electron oxidized species, 1+ and 2+, can be generated quantitatively either electrochemically or chemically with 70 % HClO4. EPR and UV/Vis spectroscopic studies and supporting DFT calculations suggest that the SOMOs of 1+ and 2+ possess thiyl radical character, whereas those of 1(py)2 + and 2(py)2 + possess formal Ni III centers. Species 2+ dimerizes at low temperature, and an X-ray crystallographic determination of the dimer [(2)2](ClO4)2.2 CH2Cl2 confirms that this dimerization involves the formation of a S-S bond (S...S=2.202(5) A).

Theoretical and electrochemical studies on organometallic symmetrical Schiff base complexes of Zn(ii), Cu(ii), Ni(ii) and Co(ii)

The electronic communication between two redox centres through a Schiff base complex has been investigated in a series of ethylenediimine-bis(1-ferrocenyl-1,3-butanedionate) complexes of Zn(II) 1, Cu(II) 2, Ni(II) 3 and Co(II) 4. Cyclic voltammetry experiments of 1 and 2 exhibit a unique two-electron reversible oxidation wave, whereas in the case of 3 and 4 two and three one-electron oxidation processes are, respectively, observed. These results suggest some electronic interaction between the iron atoms of the ferrocenyl groups. DFT calculations carried out on model complexes show that for all the studied compounds the removal of the first two electrons corresponds to the oxidation processes of the iron centres in the weakly coupled ferrocenyl termini. The electronic communication between the two iron centres increases on going from 1 to 4. Finally, a re-indexation of the bands observed in the UV-Visible spectra has been carried out using TDDFT calculations.

Trigonal-prismatic CuII6-pyrazolato cages: structural and electrochemical study, evidence of charge delocalisation

Hexanuclear CuII-complexes of formula PPN[Cu6(micro3-O)2(micro-4-Rpz)6(micro-4-R'-3,5-Ph2pz)3] have been structurally characterized and the effect of pyrazole substituents on their two consecutive one-electron oxidation processes, leading to (possibly delocalised) mixed-valent products, has been probed by cyclic voltammetry.

Cyanide-bridged linkage isomers with catecholateruthenium(ii) centres bound to Mn(i) or M(alkyne) units

Two series of stable cyanide-bridged linkage isomers, namely [(o-O2C6Cl4)(Ph3P)(OC)2Ru(mu-XY)MnL(NO)(eta-C5Me5)] (XY = CN or NC, L = CNBu(t) or CNXyl) and [(o-O2C6Cl4)L(OC)2Ru(mu-XY)M(CO)(PhC-CPh)Tp'] {M = Mo or W, L = PPh3 or P(OPh)3, Tp' = hydrotris(3,5-dimethylpyrazolyl)borate} have been synthesised; pairs of isomers are distinguishable by IR spectroscopy and cyclic voltammetry. The molecular structure of [(o-O2C6Cl4)(Ph3P)(OC)2Ru(mu-NC)Mo(CO)(PhC-CPh)Tp'] has the catecholate-bound ruthenium atom cyanide-bridged to a Mo(CO)(PhC[triple band]CPh)Tp' unit in which the alkyne acts as a four-electron donor; the alignment of the alkyne relative to the Mo-CO vector suggests the fragment (CN)Ru(CO)2(PPh3)(o-O2C6Cl4) acts as a pi-acceptor ligand. The complexes [(o-O2C6Cl4)(Ph3P)(OC)2Ru(mu-XY)Mn(NO)L(eta-C5Me5)] undergo three sequential one-electron oxidation processes with the first and third assigned to oxidation of the ruthenium-bound o-O2C6Cl4 ligand; the second corresponds to oxidation of Mn(I) to Mn(n). The complexes [(o-O2C6Cl4)L(OC)2Ru(mu-XY)M(CO)(PhC[triple band]CPh)Tp'] are also first oxidised at the catecholate ligand; the second oxidation, and one-electron reduction, are based on the M(CO)(PhC[triple band]CPh)Tp' fragment. Chemical oxidation of [(o-O,C6Cl4)(Ph3P)(OC)2Ru(mu-XY)MnL(NO)(eta-C5Me5)] with [Fe(eta-C5H4COMe)(eta-C5H5)][BF4], or of [(o-O2C6Cl4)L(OC)2Ru(mu-XY)M(CO)(PhC[triple band]CPh)Tp'] with AgBF4, gave the paramagnetic monocations [(o-O2C6Cl4)(Ph3P)(OC)2Ru(mu-XY)MnL(NO)(eta-C5Me5)]+ and [(o-O2C6Cl4)L(OC)2Ru(mu-XY)M(CO)(PhC[triple band]CPh)Tp']+, the ESR spectra of which are consistent with ruthenium-bound semiquinone ligands. Linkage isomers are distinguishable by the magnitude of the 31P hyperfine coupling constant; complexes with N-bound Ru(o-O2C6Cl4) units also show small hyperfine coupling to the nitrogen atom of the cyanide bridge.

PH-Dependence of the aqueous electrochemistry of the two-electron reduced α-[Mo18O54(SO3)] sulfite Dawson-like polyoxometalate anion derived from its triethanolammonium salt

The electrochemistry of the Dawson-like sulfite polyoxometalate anion alpha-[Mo18O54(SO3)2]6-, derived from the TEAH6{alpha-[Mo18O54(SO3)2]} salt (TEAH+ is the triethanolammonium cation; pKa=7.8), has been investigated in aqueous media using cyclic and rotated disk voltammetry at glassy carbon electrodes and bulk electrolysis, with a focus on the pH-dependence for oxidation to alpha-[Mo18O54(SO3)2]4-. In buffered media at pH>or=4, the cyclic voltammetric response for alpha-[Mo18O54(SO3)2]6- reveals two partially resolved one-electron oxidation processes corresponding to the sequential generation of alpha-[Mo18O54(SO3)2]5- and alpha-[Mo18O54(SO3)2]4-. At lower pH, using electrolytes containing sulfuric acid, the two waves coalesce but the individual apparent E0' reversible formal potential values for the two processes can be extracted down to pH 2 by assuming that reversible protonation accompanies fast electron transfer. The results for 2<or=pH<or=8 are well described by the double-square scheme mechanism: [FORMULAS: SEE TEXT] where A, B and C correspond to species alpha-[Mo18O54(SO3)2]4-, alpha-[Mo18O54(SO3)2]5- and alpha-[Mo18O54(SO3)2]6- respectively. The following thermodynamic values could be deduced: E=-0.009 V vs. Fc+/Fc; E=-0.125 V vs. Fc+/Fc and KC=1.5x10(-5) M; values for KA, KB, E and E could not be determined. Protonated alpha-[HMo18O54(SO3)2]5-, deduced to be the major species present at pH<4, is highly stable in aqueous media. In contrast, alpha-[Mo18O54(SO3)2]6-, which is dominant at higher pH values, slowly decomposes. Data considered in the context of acid-base properties of both the TEAH+ cation and alpha-[HMo18O54(SO3)2]5- anion imply that the TEAH+ cation is important in the isolation of (TEAH)6{alpha-[Mo18O54(SO3)2]}. Cyclic and rotating disk electrode voltammetries demonstrate that at least 8 electrons also can be easily added to the [Mo18O54(SO3)2]4- framework in acidic media. The existence of the electron transfer series alpha-[Mo18O54(SO3)2]4-/5-/6-/7-/8- was confirmed by cyclic voltammetric studies of water insoluble [Pn4N]4{alpha-[Mo18O54(SO3)2]} adhered to a glassy carbon electrode in contact with an aqueous 0.1 M Et4NCl electrolyte.