Control of quinone redox potentials in photosystem II: Electron transfer and photoprotection

In O(2)-evolving complex Photosystem II (PSII), an unimpeded transfer of electrons from the primary quinone (Q(A)) to the secondary quinone (Q(B)) is essential for the efficiency of photosynthesis. Recent PSII crystal structures revealed the protein environment of the Q(A/B) binding sites. We calculated the plastoquinone (Q(A/B)) redox potentials (E(m)) for one-electron reduction with a full account of the PSII protein environment. We found two different H-bond patterns involving Q(A) and D2-Thr217, resulting in an upshift of E(m)(Q(A)) by 100 mV if the H bond between Q(A) and Thr is present. The formation of this H bond to Q(A) may be the origin of a photoprotection mechanism, which is under debate. At the Q(B) side, the formation of a H bond between D2-Ser264 and Q(B) depends on the protonation state of D1-His252. Q(B) adopts the high-potential form if the H bond to Ser is present. Conservation of this residue and H-bond pattern for Q(B) sites among bacterial photosynthetic reaction centers (bRC) and PSII strongly indicates their essential requirement for electron transfer function.     

Hydrogen bonding and spin density distribution in the Qb semiquinone of bacterial reaction centers and comparison with the Qa site

In the photosynthetic reaction center from Rhodobacter sphaeroides, the primary (Q(A)) and secondary (Q(B)) electron acceptors are both ubiquinone-10, but with very different properties and functions. To investigate the protein environment that imparts these functional differences, we have applied X-band HYSCORE, a 2D pulsed EPR technique, to characterize the exchangeable protons around the semiquinone (SQ) in the Q(A) and Q(B) sites, using samples of (15)N-labeled reaction centers, with the native high spin Fe(2+) exchanged for diamagnetic Zn(2+), prepared in (1)H(2)O and (2)H(2)O solvent. The powder HYSCORE method is first validated against the orientation-selected Q-band ENDOR study of the Q(A) SQ by Flores et al. (Biophys. J.2007, 92, 671-682), with good agreement for two exchangeable protons with anisotropic hyperfine tensor components, T, both in the range 4.6-5.4 MHz. HYSCORE was then applied to the Q(B) SQ where we found proton lines corresponding to T ≈ 5.2, 3.7 MHz and T ≈ 1.9 MHz. Density functional-based quantum mechanics/molecular mechanics (QM/MM) calculations, employing a model of the Q(B) site, were used to assign the observed couplings to specific hydrogen bonding interactions with the Q(B) SQ. These calculations allow us to assign the T = 5.2 MHz proton to the His-L190 N(δ)H···O(4) (carbonyl) hydrogen bonding interaction. The T = 3.7 MHz spectral feature most likely results from hydrogen bonding interactions of O1 (carbonyl) with both Gly-L225 peptide NH and Ser-L223 hydroxyl OH, which possess calculated couplings very close to this value. The smaller 1.9 MHz coupling is assigned to a weakly bound peptide NH proton of Ile-L224. The calculations performed with this structural model of the Q(B) site show less asymmetric distribution of unpaired spin density over the SQ than seen for the Q(A) site, consistent with available experimental data for (13)C and (17)O carbonyl hyperfine couplings. The implications of these interactions for Q(B) function and comparisons with the Q(A) site are discussed.     

Substrate oxidation by copper-dioxygen adducts: mechanistic considerations

A series of copper-dioxygen adducts [{Cu(II)(MePY2)(R)}(2)(O(2))](B(C(6)F(5))(4))(2) (1(R)()), systematically varying in their electronic properties via ligand pyridyl donor substituents (R = H, MeO, and Me(2)N), oxidize a variety of substrates with varying C-H or O-H bond dissociation enthalpies. Detailed mechanistic studies have been carried out, including investigation of 1(R)() thermodynamic redox properties, 1(R)() tetrahydrofuran (THF) and N,N'-dimethylaniline (DMA) oxidation kinetics (including analyses of substrate dicopper binding equilibria), and application of mechanistic probes (N-cyclopropyl-N-methylaniline (CMA) and (p-methoxyphenyl)-2,2-dimethylpropanol (MDP)), which can distinguish if proton-coupled electron-transfer (PCET) processes proceed through concerted electron-transfer proton-transfer (ETPT) or consecutive electron-transfer proton-transfer (ET/PT) pathways. The results are consistent with those of previous complementary studies; at low thermodynamic driving force for substrate oxidation, an ET/PT is operable, but once ET (i.e., substrate one-electron oxidation) becomes prohibitively uphill, the ETPT pathway occurs. Possible differences in coordination structures about 1(Me)()()2(N)()/1(MeO)() compared to those of 1(H)() are also used to rationalize some of the observations.     

Structures and energetics of hydrated oxygen anion clusters

Hydration of the atomic oxygen radical anion is studied with computational electronic structure methods, considering (O(-))(H(2)O)(n) clusters and related proton-transferred (OH(-))(OH)(H(2)O)(n)(-)(1) clusters having n = 1-5. A total of 67 distinct local-minimum structures having various interesting hydrogen bonding motifs are obtained and analyzed. On the basis of the most stable form of each type, (O(-))(H(2)O)(n)) clusters are energetically favored, although for n > or = 3, there is considerable overlap in energy between other members of the (O(-))(H(2)O)(n) family and various members of the (OH(-))(OH)(H(2)O)(n)(-)(1) family. In the lower-energy (O(-))(H(2)O)(n) clusters, the hydrogen bonding arrangement about the oxygen anion center tends to be planar, leaving the oxygen anion p-like orbital containing the unpaired electron uninvolved in hydrogen bonding with any water molecule. In (OH(-))(OH)(H(2)O)(n)(-)(1) clusters, on the other hand, nonplanar arrangements are the rule about the anionic oxygen center that accepts hydrogen bonds. No instances are found of OH(-) acting as a hydrogen bond donor. Those OH bonds that form hydrogen bonds to an anionic O(-) or OH(-) center are significantly stretched from their equilibrium value in isolated water or hydroxyl. A quantitative inverse correlation is established for all hydrogen bonds between the amount of the OH bond stretch and the distance to the other oxygen involved in the hydrogen bond.     

Redox properties of undoped 5 nm diamond nanoparticles

This paper demonstrates the promoting effects of 5 nm undoped detonation diamond nanoparticles on redox reactions in solution. An enhancement in faradaic current for the redox couples Ru(NH(3))(6)(3+/2+) and Fe(CN)(6)(4-/3-) was observed for a gold electrode modified with a drop-coated layer of nanodiamond (ND), in comparison to the bare gold electrode. The ND layer was also found to promote oxygen reduction. Surface modification of the ND powders by heating in air or in a hydrogen flow resulted in oxygenated and hydrogenated forms of the ND, respectively. Oxygenated ND was found to exhibit the greatest electrochemical activity and hydrogenated ND the least. Differential pulse voltammetry of electrode-immobilised ND layers in the absence of solution redox species revealed oxidation and reduction peaks that could be attributed to direct electron transfer (ET) reactions of the ND particles themselves. It is hypothesised that ND consists of an insulating sp(3) diamond core with a surface that has significant delocalised pi character due to unsatisfied surface atoms and C[double bond, length as m-dash]O bond formation. At the nanoscale surface properties of the particles dominate over those of the bulk, allowing ET to occur between these essentially insulating particles and a redox species in solution or an underlying electrode. We speculate that reversible reduction of the ND may occur via electron injection into available surface states at well-defined reduction potentials and allow the ND particles to act as a source and sink of electrons for the promotion of solution redox reactions.     

Roles of the proximal hydrogen bonding network in cytochrome P450cam-catalyzed oxygenation

Structural and functional roles of the hydrogen bonding network that surrounds the heme-thiolate coordination of P450(cam) from Pseudomonas putida were investigated. A hydrogen bond between the side chain amide of Gln360 and the carbonyl oxygen of the axial Cys357 was removed in Q360L. The side chain hydrogen bond and the electrostatic interaction between the polypeptide amide proton of Gln360 and the sulfur atom of Cys357 were simultaneously removed in Q360P. The increased electron donation of the axial thiolate in Q360L and Q360P was evidenced by negative shifts of their reduction potentials by 45 and 70 mV, respectively. Together with the results on L358P in which the amide proton at position 358 was removed (Yoshioka, S., Takahashi, S., Ishimori, K., Morishima, I. J. Inorg. Biochem. 2000, 81, 141-151), we propose that the side chain hydrogen bond and the electrostatic interaction of the amide proton with the thiolate ligand cause approximately 45 and approximately 35 mV of positive shifts, respectively, of the redox potential of the heme in P450(cam). The resonance Raman spectra of the ferrous-CO form of the Q360 mutants showed a downshifted Fe-CO stretching mode at 482 approximately 483 cm(-)(1) compared with that of wild-type P450(cam) at 484 cm(-)(1). The Q360 mutants also showed the upshift by 4 approximately 5 cm(-)(1) of the Fe-NO stretching mode in the ferrous-NO form. These Raman results indicate the increase in the sigma-electron donation of the thiolate ligand in the reduced state of the Q360 mutants and were in contrast to the increased pi-back-donation of the thiolate in L358P having an upshifted Fe-CO stretching mode at 489 cm(-)(1). The catalytic activities of the Q360 mutants for the unnatural substrates were similar to those of the wild-type enzyme, indicating that the increased sigma-electron donation does not promote the O-O bond heterolysis in the Q360 mutants, although the increased pi-electron donation in L358P promoted the heterolysis of the O-O bond. We conclude that the functions of the proximal hydrogen bonding network in P450(cam) are to stabilize the heme-thiolate coordination, and to regulate the redox potential of the heme iron. Furthermore, we propose that the pi-electron donation, not the sigma-electron donation, of the thiolate ligand promotes the heterolysis of the O-O bond of dioxygen.     

Cyanil](2)(2-) dimers possess long, two-electron ten-center (2e(-)/10c) multicenter bonding

A long, two-electron ten-center (2e(-)/10c) [8 carbon plus 2 oxygen] bond in diamagnetic dimers of radical-anion tetracyano-1,4-benzoquinoneide (cyanil, [Q] (-)), [Q](2)(2-), is described by B3LYP and CASSCF(2,2)/MCQDPT calculations.     

Mimicking protein-protein electron transfer: voltammetry of Pseudomonas aeruginosa azurin and the Thermus thermophilus Cu(A) domain at omega-derivatized self-assembled-monolayer gold electrodes

Well-defined voltammetric responses of redox proteins with acidic-to-neutral pI values have been obtained on pure alkanethiol as well as on mixed self-assembled-monolayer (SAM) omega-derivatized alkanethiol/gold bead electrodes. Both azurin (P. aeruginosa) (pI = 5.6) and subunit II (Cu(A) domain) of ba(3)-type cytochrome c oxidase (T. thermophilus) (pI = 6.0) exhibit optimal voltammetric responses on 1:1 mixtures of [H(3)C(CH(2))(n)()SH + HO(CH(2))(n)()SH] SAMs. The electron transfer (ET) rate vs distance behavior of azurin and Cu(A) is independent of the omega-derivatized alkanethiol SAM headgroups. Strikingly, only wild-type azurin and mutants containing Trp48 give voltammetric responses: based on modeling, we suggest that electronic coupling with the SAM headgroup (H(3)C- and/or HO-) occurs at the Asn47 side chain carbonyl oxygen and that an Asn47-Cys112 hydrogen bond promotes intramolecular ET to the copper. Inspection of models also indicates that the Cu(A) domain of ba(3)-type cytochrome c oxidase is coupled to the SAM headgroup (H(3)C- and/or HO-) near the main chain carbonyl oxygen of Cys153 and that Phe88 (analogous to Trp143 in subunit II of cytochrome c oxidase from R. sphaeroides) is not involved in the dominant tunneling pathway. Our work suggests that hydrogen bonds from hydroxyl or other proton-donor groups to carbonyl oxygens potentially can facilitate intermolecular ET between physiological redox partners.     

A theoretical study of reactivity and regioselectivity in the hydroxylation of adamantane by ferrate(VI)

The conversion of adamantane to adamantanols mediated by ferrate (FeO(4)(2)(-)), monoprotonated ferrate (HFeO(4)(-)), and diprotonated ferrate (H(2)FeO(4)) is discussed with the hybrid B3LYP density functional theory (DFT) method. Diprotonated ferrate is the best mediator for the activation of the C-H bonds of adamantane via two reaction pathways, in which 1-adamantanol is formed by the abstraction of a tertiary hydrogen atom (3 degrees ) and 2-adamantanol by the abstraction of a secondary hydrogen atom (2 degrees ). Each reaction pathway is initiated by a C-H bond cleavage via an H-atom abstraction that leads to a radical intermediate, followed by a C-O bond formation via an oxygen rebound step to lead to an adamantanol complex. The activation energies for the C-H cleavage step are 6.9 kcal/mol in the 1-adamantanol pathway and 8.4 kcal/mol in the 2-adamantanol pathway, respectively, at the B3LYP/6-311++G level of theory, whereas those of the second reaction step corresponding to the rebound step are relatively small. Thus, the rate-determining step in the two pathways is the C-H bond dissociation step, which is relevant to the regioselectivity for adamantane hydroxylation. The relative rate constant (3 degrees )/(2 degrees ) for the competing H-atom abstraction reactions is calculated to be 9.30 at 75 degrees C, which is fully consistent with an experimental value of 10.1.     

Valence and spin situations in isomeric [(bpy)Ru(Q')2]n (Q' = 3,5-di-tert-butyl-N-aryl-1,2-benzoquinonemonoimine). An experimental and DFT analysis

The article deals with the ruthenium complexes, [(bpy)Ru(Q')(2)] (1-3) incorporating two unsymmetrical redox-noninnocent iminoquinone moieties [bpy = 2,2'-bipyridine; Q' = 3,5-di-tert-butyl-N-aryl-1,2-benzoquinonemonoimine, aryl = C(6)H(5) (Q'(1)), 1; m-Cl(2)C(6)H(3) (Q'(2)), 2; m-(OCH(3))(2)C(6)H(3) (Q'(3)), 3]. 1 and 3 have been preferentially stabilised in the cc-isomeric form while both the ct- and cc-isomeric forms of 2 are isolated [ct: cis and trans and cc: cis and cis with respect to the mutual orientations of O and N donors of two Q']. The isomeric identities of 1-3 have been authenticated by their single-crystal X-ray structures. The collective consideration of crystallographic and DFT data along with other analytical events reveals that 1-3 exhibit the valence configuration of [(bpy)Ru(II)(Q'(Sq))(2)]. The magnetization studies reveal a ferromagnetic response at 300 K and virtual diamagnetic behaviour at 2 K. DFT calculations on representative 2a and 2b predict that the excited triplet (S = 1) state is lying close to the singlet (S = 0) ground state with singlet-triplet separation of 0.038 eV and 0.075 eV, respectively. In corroboration with the paramagnetic features the complexes exhibit free radical EPR signals with g～2 and (1)HNMR spectra with broad aromatic proton signals associated with the Q' at 300 K. Experimental results in conjunction with the DFT (for representative 2a and 2b) reveal iminoquinone based preferential electron-transfer processes leaving the ruthenium(ii) ion mostly as a redox insensitive entity: [(bpy)Ru(II)(Q'(Q))(2)](2+) (1(2+)-3(2+)) ? [(bpy)Ru(II)(Q(')(Sq))(Q(')(Q))](+) (1(+)-3(+)) ? [(bpy)Ru(II)(Q(')(Sq))(2)] (1-3) ? [(bpy)Ru(II)(Q(')(Sq))(Q(')(Cat))](-)/[(bpy)Ru(III)(Q(')(Cat))(2)](-) (1(-)-3(-)). The diamagnetic doubly oxidised state, [(bpy)Ru(II)(Q'(Q))(2)](2+) in 1(2+)-3(2+) has been authenticated further by the crystal structure determination of the representative [(bpy)Ru(II)(Q'(3))(2)](ClO(4))(2) [3](ClO(4))(2) as well as by its sharp (1)H NMR spectrum. The key electronic transitions in each redox state of 1(n)-3(n) have been assigned by TD-DFT calculations on representative 2a and 2b.     

Electrochemically controlled hydrogen bonding. Nitrobenzenes as simple redox-dependent receptors for arylureas

Reduction of nitrobenzene derivatives in the presence of arylureas in aprotic solvents results in large positive shifts in potential of the nitrobenzene(0/)(-) cyclic voltammetry wave with little change in wave shape. This behavior is indicative of reversible hydrogen bonding between nitrobenzene radical anions and arylureas. Computer fitting of the cyclic voltammetry of 4-nitroaniline, NA, plus 1,3-diphenylurea in DMF shows essentially no binding between urea and NA in the oxidized state (K(ox) < 1 M(-)(1)), but very strong binding in the reduced state (K(red) = 8 x 10(4) M(-)(1)), along with very rapid rates of hydrogen bond formation (k(f)'s approximately 10(8)-10(10) M(-)(1) s(-)(1)), making this system a fast on/off redox switch.     

Interfacial bridge-mediated electron transfer: mechanistic analysis based on electrochemical kinetics and theoretical modelling

Understanding the physical and chemical factors that control the kinetics of interfacial electron-transfer (ET) reactions is important for a large number of technological applications. The present article describes electrochemical kinetic studies of these factors, in which standard interfacial ET rate constants (k(0)(l)) have been measured for ET between substrate Au electrodes and various redox couples attached to the electrode surfaces by variable lengths (l) of oligomethylene (OM), oligophenylenevinylene (OPV) and oligophenyleneethynylene (OPE) bridges, which were constituents of mixed self-assembled monolayers (SAMs). The k(0)(l) measurements employed the indirect laser-induced temperature jump (ILIT) technique, which permits the measurement of interfacial ET rates that are orders of magnitude faster than those measurable by conventional techniques using the macroelectrodes that are the most convenient substrates for the mixed SAMs. The robustness of the measured rate constants (k(0)(l)), together with the Arrhenius activation energies (E(a)(l)) and preexponential factors (A(l)), is demonstrated by their invariance with respect to several experimental system parameters (including the chemical nature and length of the diluent component of the mixed SAM). Analysis of the kinetic results demonstrates that all of the observed interfacial ET processes proceed through a common type of transition state (predominantly associated with solvent reorganization around the redox moiety) and that the actual ET step involves direct electronic tunnelling between the Au electrode and the redox moiety. However, for the full range of l investigated, a global exponential decay of A(l) is not found for any of the three types of bridges. Possible reasons for this behavior, including the role of rate determining steps associated with adiabatic mechanisms within or beyond the transition state theory framework, are discussed, and comparisons with related conductance measurements are presented.     

Ultrafast forward and backward electron transfer dynamics of coumarin 337 in hydrogen-bonded anilines as studied with femtosecond UV-pump/IR-probe spectroscopy

Femtosecond infrared spectroscopy is used to study both forward and backward electron transfer (ET) dynamics between coumarin 337 (C337) and the aromatic amine solvents aniline (AN), N-methylaniline (MAN), and N,N-dimethylaniline (DMAN), where all the aniline solvents can donate an electron but only AN and MAN can form hydrogen bonds with C337. The formation of a hydrogen bond with AN and MAN is confirmed with steady state FT-IR spectroscopy, where the C═O stretching vibration is a direct marker mode for hydrogen bond formation. Transient IR absorption measurements in all solvents show an absorption band at 2166 cm(-1), which has been attributed to the C≡N stretching vibration of the C337 radical anion formed after ET. Forward electron transfer dynamics is found to be biexponential with time constants τ(ET)(1) = 500 fs, τ(ET)(2) = 7 ps in all solvents. Despite the presence of hydrogen bonds of C337 with the solvents AN and MAN, no effect has been found on the forward electron transfer step. Because of the absence of an H/D isotope effect on the forward electron transfer reaction of C337 in AN, hydrogen bonds are understood to play a minor role in mediating electron transfer. In contrast, direct π-orbital overlap between C337 and the aromatic amine solvents causes ultrafast forward electron transfer dynamics. Backward electron transfer dynamics, in contrast, is dependent on the solvent used. Standard Marcus theory explains the observed backward electron transfer rates.     

Different hydrogen-bonding patterns in two [Zn(ENTPP)] complexes with water or methanol as ligands

We have synthesized zinc complexes of H₂ENTPP (5-(8-ethoxycarbonyl-1-naphthyl)-10,15,20-triphenyl porphyrin) as a model to study hydrogen-bonding interactions. When water or methanol is a ligand, crystals of [Zn(ENTPP)(CH₃OH)] or [Zn(ENTPP)(H₂O)]?·?C₆H₅CH₃ were obtained. In both structures, the ligand has hydrogen-bonding interactions, but in different patterns. In [Zn(ENTPP)(CH₃OH)], the methanol oxygen and carboxylate oxygen in the naphthyl group form an intermolecular hydrogen bond. In [Zn(ENTPP)(H₂O)]?·?C₆H₅CH₃, there are two independent molecules A and B. In molecule B, there is an intramolecular hydrogen bond between the water oxygen and the carboxylate oxygen, while in molecule A, besides the intramolecular hydrogen bond, there is an intermolecular hydrogen bond between the water oxygen and the carboxylate oxygen. ¹H NMR spectra suggest the binding of methanol or water to zinc are equilibrium processes in solution. Equilibrium constant has been determined by UV-Vis measurements, and it suggests the binding affinity of zinc to methanol has been moderately increased.     

Hydride Ligands Make the Difference: Density Functional Study of the Mechanism of the Murai Reaction Catalyzed by [Ru(H)(2) (H(2) )(2) (PR(3) )(2) ] (R=cyclohexyl)

The catalytic cycle for the Murai reaction at room temperature between ethylene and acetophenone catalyzed by [Ru(H)(2) (H(2) )(2) (PMe(3) )(2) ] has been studied computationally at the B3PW91 level. The active species is the ruthenium dihydride complex [Ru(H)(2) (PMe(3) )(2) ]. Coordination of the ketone group to Ru induces very easy C?H bond cleavage. Coordination of ethylene after ketone de-coordination, followed by ethylene insertion into a Ru?H bond, creates the Ru?ethyl bond. Isomerization of the complex to a Ru(IV) intermediate creates the geometry adapted to C?C bond formation. Re-coordination of the ketone before the C?C coupling lowers the energy of the corresponding TS. The highest point on the potential energy surface (PES) is the TS for the isomerization to the Ru(IV) intermediate, which prepares the catalyst geometry for the C?C coupling step. Inclusion of dispersion corrections significantly lowers the height of the overall activation barrier. The actual bond cleavage and bond forming processes are associated to low activation barriers because of the presence of hydrogen atoms around the Ru center. They act as redox buffers through formation and breaking of H?H bonds in the coordination sphere. This flexibility allows optimal repartition of the various ligands according to the change in stereoelectronic demands along the catalytic cycle.     

Evaluating the solvation properties of functionalized ionic liquids with varied cation/anion composition using the solvation parameter model

Ionic liquids (ILs) are promising gas chromatography (GC) stationary phases due to their high thermal stability, negligible vapor pressure, and ability to solvate a broad range of analytes. The tunability of ILs allows for structure modification in pursuit of enhanced separation selectivity and control of analyte elution order. In this study, the solvation parameter model is used to characterize the solvation interactions of fifteen ILs containing various cationic functional groups (i.e., dimethylamino, hydroxyl, and ether) and cation types paired with various counter anions, namely, tris(pentafluoroethyl)trifluorophosphate (FAP(-)), bis[(trifluoromethyl)sulfonyl]imide (NTf(2)(-)), thiocyanate (SCN(-)), tricyanomethide (C(CN)(3)(-)), tetracyanoborate (B(CN)(4)(-)), and bis[oxalate(2-)]borate (BOB(-)). The presence of functional groups affected the hydrogen bond basicity, hydrogen bond acidity, as well as dispersion interactions of the resulting ILs, while the change of cation type yielded modest influence on the dipolarity. The switch of counter anions in unfunctionalized ILs produced compounds with higher dipolarity and hydrogen bond basicity. The dipolarity and hydrogen bond basicity of ILs possessing cyano-containing anions appeared to be inversely proportional to the cyano content of the anion. The modification of IL structure resulted in a significant effect on the retention behavior as well as separation selectivity for many solutes, including reversed elution orders of some analytes. This study provides one of the most comprehensive examinations up-to-date on the relation between IL structure and the resulting solvation characteristics and gives tremendous insight into choosing suitable ILs as GC stationary phases for solute specific separations.     

Synthesis, characterization, and electronic structure of new type of heterometallic boride clusters

The reaction of [Cp*TaCl(4)], 1 (Cp* = η(5)-C(5)Me(5)), with [LiBH(4)·THF] at -78 °C, followed by thermolysis in the presence of excess [BH(3)·THF], results in the formation of the oxatantalaborane cluster [(Cp*Ta)(2)B(4)H(10)O], 2 in moderate yield. Compound 2 is a notable example of an oxatantalaborane cluster where oxygen is contiguously bound to both the metal and boron. Upon availability of 2, a room temperature reaction was performed with [Fe(2)(CO)(9)], which led to the isolation of [(Cp*Ta)(2)B(2)H(4)O{H(2)Fe(2)(CO)(6)BH}], 3. Compound 3 is an unusual heterometallic boride cluster in which the [Ta(2)Fe(2)] atoms define a butterfly framework with one boron atom lying in a semi-interstitial position. Likewise, the diselenamolybdaborane, [(Cp*Mo)(2)B(4)H(4)Se(2)], 4 was treated with an excess of [Fe(2)(CO)(9)] to afford the heterometallic boride cluster [(Cp*MoSe)(2)Fe(6)(CO)(13)B(2)(BH)(2)], 5. The cluster core of 5 consists of a cubane [Mo(2)Se(2)Fe(2)B(2)] and a tricapped trigonal prism [Fe(6)B(3)] fused together with four atoms held in common between the two subclusters. In the tricapped trigonal prism subunit, one of the boron atoms is completely encapsulated and bonded to six iron and two boron atoms. Compounds 2, 3, and 5 have been characterized by mass spectrometry, IR, (1)H, (11)B, (13)C NMR spectroscopy, and the geometric structures were unequivocally established by crystallographic analysis. The density functional theory calculations yielded geometries that are in close agreement with the observed structures. Furthermore, the calculated (11)B NMR chemical shifts also support the structural characterization of the compounds. Natural bond order analysis and Wiberg bond indices are used to gain insight into the bonding patterns of the observed geometries of 2, 3, and 5.     

Structural dependence of microwave dielectric properties of ixiolite structured ZnTiNb2O8 materials: crystal structure refinement and Raman spectra study

Structural and property relationships of ixiolite structured ZnTiNb(2)O(8) microwave dielectric materials were studied by structure refinement and Raman spectra analysis. The vibration modes which have Raman activities of the ixiolite structure were assigned for the first time. The bands with wavenumbers greater than 450 cm(-1) can be associated with several modes (A(g(2)), B(3g(1)), B(3g(2)), A(g(1)), B(1g(2)), A(g(3)), B(2g(2))) involving the stretching of the cation-O bonds. For wavenumbers between 250 and 450 cm(-1), the bands are due, principally, to the bending of O-cation-O (B(1g(1)), B(2g(1)), B(1g(3))). The origin of the bands with wavenumbers below 250 cm(-1) would be lattice vibrations (B(1g(4)), A(g(4)), B(3g(4)), B(2g(4))), mainly associated with cation ions. The correlation between bond strength and packing fraction, Raman shift, full width at half maximum (FWHM) of Raman spectra were discussed. With increase of bond strength, the oxygen octahedron became rigid, the Raman shift increased, and the damping behavior became weaker. With increase of Raman shift, the dielectric constant decreased. With increase of packing fraction and decrease of FWHM, the Q(f) (quality factor × resonance frequency) value increased. The τ(f) (temperature coefficient of resonance frequency) decreased with increase of bond strength. And there was no direct relationship between oxygen octahedron distortion and τ(f). The excellent microwave dielectric properties of ZnTiNb(2)O(8) in this work were: dielectric constant (ε) = 34.4, Q(f) = 56,900 GHz, τ(f) = -47.94 × 10(-6)/°C.     

Effect of alkyl substitueras in hydrophobic 8-quinolinol on the extraction of gallium(III) and applications to the separation of gallium(III) from aluminum(III)

The extraction of gallium(III) with newly prepared 5-alkyloxymethyl-8-quinolinol derivatives with alkyl substituent at the 2-position in 8-quinolinol moiety has been studied. The Ga(III)-5-octyloxymethyl-8-quinolinol (HO(8)Q), Ga(III)-2-methyl-5-octyloxymethyl-8-quinolinol (HMO(8)Q), Ga(III)-2-methyl-5-hexyloxymethyl-8-quinolinol (HM-O(6)Q), and Ga(HI)-2-n-butyl-5-hexyloxymethyl-8-quinolinol (HNBO(6)Q) complexes extracted in heptane from a perchloric acid medium were Ga(O(8)Q)(3), Ga(OH)(H(2)O)(MO(8)Q)(2), Ga(OH)(H(2)O)(MO(6)Q)(2) and Ga(OH)H(2)O)(NBO(6)Q)(2), respectively. The 2-tert-butyl-5-hexyloxymethyl-8-quinolinol did not exhibit any reactivity toward gallium(III). The extraction constants for Ga(O(8)Q)(3) (K(ex) = [Ga(O(8)Q)(3)](org) [H(+)](3)/[Ga(3+)][HO(8)Q](org)(3)), Ga(OH)(H(2)O)(MO(8)Q)(2) (K(ex) = [Ga(OH) (H(2)O)(MO(8)Q)(2)](org) [H(+)](3)/[Ga(3+)][HMO(8)Q](org)(2)), Ga(OH)(H(2)O)(2)(MO(6)Q)(2) and Ga(OH)(H(2)O)(NBO(6)Q)(2), which were extracted in heptane from an acidic solution, are 10(3.21 +/- 0.12), 10(-4.24 +/- 0.16), 10(-3.84 +/- 0.16) and 10(-4.07 +/- 0.07), respectively at I = 0.1 M and 25 degrees C. HNBO(6)Q exhibited very high selectivity toward gallium(III) in the presence of aluminum(III). Even in the presence of a 100 fold excess of aluminum(III) to gallium(III) (1.43 x 10(-5) M), gallium(III) was completely extracted and the distribution ratio of aluminum(III) was found to be less than 2.0 x 10(-3).     

Ions in water: the microscopic structure of concentrated NaOH solutions

A neutron diffraction experiment with isotopic H/D substitution on four concentrated NaOH/H(2)O solutions is presented. The full set of partial structure factors is extracted, by combining the diffraction data with a Monte Carlo simulation. These allow to investigate both the changes of the water structure in the presence of ions and their solvation shells. It is found that the interaction with the solute affects the tetrahedral network of hydrogen bonded water molecules in a manner similar to the application of high pressure to pure water. The solvation shell of the OH(-) ions has an almost concentration independent structure, although with concentration dependent coordination numbers. The hydrogen site coordinates a water molecule through a weak bond, while the oxygen site forms strong hydrogen bonds with a number of molecules that is on the average very close to four at the higher water concentrations and decreases to about three at the lowest one. The competition between hydrogen bond interaction and Coulomb forces in determining the orientation of water molecules within the cation solvation shell is visible in the behavior of the g(NaHw)(r) function