Osmium Complexes Research Articles

A miniaturized voltammetric pH sensor based on optimized redox polymers

A miniaturized pH sensor based on the voltammetric determination of the potential difference between a pH dependent toluidine blue O modified redox polymer and a pH independent osmium complex modified redox polymer was developed. Gold micro electrodes of various dimensions were modified with the two redox polymers by non-manual deposition procedures. Square wave voltammetry was used to determine the oxidation potentials of the polymer bound redox species allowing the precise determination of the pH value of the electrolyte solution without the need of a stable reference electrode.

Immobilisation of Alkylamine-Functionalised Osmium Redox Complex on Glassy Carbon using Electrochemical Oxidation

The electrochemical oxidation of alkylamines provides a method for modification of carbon, and other surfaces via formation of a radical amine that reacts with the surface. Direct electrochemical oxidation of an alkylamine functional group of a redox complex provides a simple route to preparation of a redox active layer on carbon surfaces. Here we report on oxidation of an osmium redox complex, containing an alkylamine ligand distal to the metal co-ordination site, on carbon electrodes to directly produce a redox active film on the surface. The presence of the redox-active layer of osmium complexes is confirmed by cyclic voltammetry and X-Ray photoelectron spectroscopy. The average surface coverage of the attached film upon electrolysis of an [Os(2,2′-bipyridine)2(4-aminomethylpyridine)Cl].PF6 complex is 0.84 (± 0.3)×10−10 moles cm−2, demonstrating that coverages close to that predicted for a close-packed monolayer of complex is attained. The bioelectrocatalytic activity of the modified electrode was evaluated for oxidation of glucose in presence of glucose oxidase in solution. Hence, electrochemical coupling of alkylamine functionalised osmium redox complexes provides a simple and efficient methodology for obtaining redox active monolayers on carbon surfaces with potential applications to biosensor and biofuel cell device development.

StrainedansaHalf-Sandwich Complexes of Ruthenium and Osmium and a Non-Iron Metallopolymer by Ring-Opening Polymerization

Herein we report the first non-iron polymer obtained from an ansa half-sandwich complex. This polymeric organometallic material was obtained from a new disilanediyl-bridged ruthenium complex upon thermally induced ring-opening polymerization (ROP). Additionally, a corresponding distannanediyl-bridged osmium species is reported, the first example of an ansa half-sandwich complex of this element.

Metal‐Only Lewis Pairs by Reversible Insertion of Ruthenium and Osmium Fragments into Metal–Boron Double Bonds

New metal-only Lewis pairs (MOLPs: Ru→Cr and Os→Cr) are prepared by the insertion of a zerovalent ruthenium or osmium complex into chromium-boron double bonds of borylene complexes. The reaction creates new borylene complexes (the first ever for osmium), and is crystallization-controlled; re-dissolving the complexes results in regeneration of the starting materials. A mechanism is proposed based on DFT calculations, along with a computational study of the unusual MOLPs.

M‐Metallaphenol: Synthesis and Reactivity Studies

Treatment of the osmium complex [Os{CHC-(PPh3 )CH(OH)-η(2) -C≡CH}(PPh3 )2 (NCS)2 ] (1) with excess triethylamine produces the first m-metallaphenol complex [Os{CHC(PPh3 )CHC(OH)CH}(PPh3 )2 (NCS)2 ] (2). The NMR spectroscopic and structural data as well as the nucleus-independent chemical-shift (NICS) values suggest that osmaphenol 2 has aromatic character. The reactivity studies demonstrate that 2 can react with different isocyanates to form the annulation reaction products [Os{CHC(PPh3 )CHC(OCONR)C}(PPh3 )2 (NCS)2 ] (R=Ph (3), iPr (7), Bn (8)) via the carbamate intermediates [Os{CHC(PPh3 )CHC(O-CONHR)CH}(PPh3 )2 (NCS)2 ] (R=Ph (4), iPr (5), Bn (6)). In addition, the similar annulation reactions can be extended to other unsaturated compounds containing N-C multiple bonds, for example, isothiocyanates, pyridine, and sodium thiocyanate, which can produce the corresponding fused osmabenzene complexes. In contrast, the reactions of 2 with common electrophiles, such as NOBF4 , NO2 BF4 , N-bromosuccinimide, and N-chlorosuccinimide only led to the decomposition of the metallaphenol ring. The experimental results suggest that 2 is very electrophilic and readily reacts with nucleophiles, which is mainly due to the metal center and the strong electron-withdrawing phosphonium group.

Density Functional Theory Study of Oxygen-Atom Insertion into Metal–Methyl Bonds of Iron(II), Ruthenium(II), and Osmium(II) Complexes: Study of Metal-Mediated C–O Bond Formation

Metal-mediated C-O bond formation is a key step in hydrocarbon oxygenation catalytic cycles; however, few examples of this reaction have been reported for low-oxidation-state complexes. Oxygen insertion into a metal-carbon bond of Cp*M(CO)(OPy)R (Cp* = η(5)-pentamethylcyclopentadienyl; R = Me, Ph; OPy = pyridine-N-oxide; M = Fe, Ru, Os) was analyzed via density functional theory calculations. Oxygen-atom insertions through a concerted single-step organometallic Baeyer-Villiger pathway and a two-step pathway via a metal-oxo intermediate were studied; calculations predict that the former pathway was lower in energy. The results indicated that functionalization of M-R to M-OR (R = Me, Ph) is plausible using iron(II) complexes. Starting from Cp*Fe(CO)(OPy)Ph, the intermediate Fe-oxo showed oxyl character and, thus, is best considered an Fe(III)O(•-) complex. Oxidation of the π-acid ancillary ligand CO was facile. Substitutions of CO with dimethylamide and NH3 were calculated to lower the activation barrier by ∼1-2 kcal/mol for formation of the Fe(III)O(•-) intermediate, whereas a chloride ligand raised the activation barrier to 26 kcal/mol from 22.9 kcal/mol.

High-throughput real-time electrochemical monitoring of LAMP for pathogenic bacteria detection

One of the significant challenges in healthcare is the development of point-of-care (POC) diagnostics. POC diagnostics require low-cost devices that offer portability, simplicity in operation and the ability for high-throughput and quantitative analysis. Here, we present a novel roll-to-roll ribbon fluid-handling device for electrochemical real-time monitoring of nucleic acid (NA) amplification and bacteria detection. The device rendered loop-mediated isothermal amplification (LAMP) and real-time electrochemical detection based on the interaction between LAMP amplicon and the redox-reactive osmium complex. We have shown the detection of 30CFU/ml of Escherichia coli (in the range between 30 and 3×107CFU/ml) and 200CFU/ml of Staphylococcus aureus (in the range of 200–2×105CFU/ml) cultured samples in both real-time and end point detection. This device can be used for the detection of various Gram-negative and a number of Gram-positive bacterial pathogens with high sensitivity and specificity in a high-throughput format. Using a roll-to-roll cassette approach, we could detect 12 samples in one assay. Since the LAMP and electrochemical analysis are implemented within sealed flexible biochips, time-consuming processing steps are not required and the risk of contamination is significantly reduced.

Osmium-Promoted Dehydrogenation of Amine–Boranes and B–H Bond Activation of the Resulting Amino–Boranes

The five-coordinate osmium complex OsH(SH)(CO)(PiPr3)2, containing an electrophilic center bonded to the soft hydrogen sulfide ligand, promotes dehydrogenation of amine–boranes and captures the amino–borane products, forming hydrogenaminothioborate complexes.

ChemInform Abstract: Osmium(III) and Osmium(V) Complexes Bearing a Macrocyclic Ligand: A Simple and Efficient Catalytic System for cis‐Dihydroxylation of Alkenes with Hydrogen Peroxide.

A simple protocol that uses [Os(III)(OH)(H2O)(L-N4Me2)](PF6)2 (1; L-N4Me2 = N,N'-dimethyl-2,11-diaza[3.3](2,6)pyridinophane) as a catalyst and H2O2 as a terminal oxidant for efficient cis-1,2-dihydroxylation of alkenes is presented. Unfunctionalized (or aliphatic) alkenes and alkenes/styrenes containing electron-withdrawing groups are selectively oxidized to the corresponding vicinal diols in good to excellent yields (46-99 %). In the catalytic reactions, the stoichiometry of alkene:H2O2 is 1:1, and thus the oxidant efficiency is very high. For the dihydroxylation of cyclohexene, the catalytic amount of 1 can be reduced to 0.01 mol % to achieve a very high turnover number of 5500. The active oxidant is identified as the Os(V)(O)(OH) species (2), which is formed via the hydroperoxide adduct, an Os(III)(OOH) species. The active oxidant 2 is successfully isolated and crystallographically characterized.

A glance at the reactivity of osma(II)cycles [Os(C–N)x(bpy)3 − x]m + (x = 0–3) Covering a 1.8 V Potential Range toward Peroxidase through Monte Carlo Simulations (−C–N = o-2-phenylpyridinato, bpy = 2,2′-bipyridine)

Three cyclometalated and one coordination compounds [Os(C–N)x(bpy)3−x]m (x/m=0/2+ (4); 1/1+ (3); 2/1+ (2); 3/0 (1); −C–N=2-phenylpyridinato, bpy=2,2′-bipyridine) with drastically different reduction potentials have been used for analyzing the second-order rate constants for one-electron, metal-based osmium(II) to osmium(III) oxidation of the complexes by compound I (k2) and compound II (k3) of horseradish peroxidase. Previously unknown k2 and k3 have been determined by digital simulation of cyclic voltammograms measured in phosphate buffer of pH7.6 and 21±1°C. Osmium(II) species derived from osmium(III) complexes 1 and 2 were generated electrochemically in situ. Under the conditions used the reduction potentials for the OsIII/II feature equal −0.90, −0.095, 0.23 and 0.85V versus NHE (normal hydrogen electrode) for 1–4, respectively. The rate constants k2 equal ~5×107, 6×108, 2×106 and 1×105M−1s−1 and the rate constants k3 equal ~9×106, 4×107, 1×106 and 1×105M−1s−1 for complexes 1–4, respectively. Both rate constants k2 and k3 first increase with increasing the reaction driving force on going from 4 to 2 but then both decrease on going to complex 1 though the reaction driving force is the highest in this case. The system described has been explored theoretically using docking Monte Carlo simulations.

Magnetic bead-based hybridization assay for electrochemical detection of microRNA

Aberrant expression of microRNAs (miRNAs), short non-coding RNA molecules regulating gene expression, is often found in tumor cells, making the miRNAs suitable candidates as cancer biomarkers. Electrochemistry is an interesting alternative to current standard methods of miRNA detection by offering cheaper instrumentation and faster assays times. In this paper, we labeled miRNA in a quick, simple, two-step procedure with electroactive complex of osmium(VI) and 2,2′-bipyridine, Os(VI)bipy, which specifically binds to the ribose at the 3′-end of the miRNA, and hybridized such labeled miRNA with biotinylated capture probe attached to the streptavidin magnetic beads. Labeled miRNA was then detected at hanging mercury drop electrode at femtomole level due to an electrocatalytic nature of the peak from the Os(VI)bipy label. We obtained good selectivity of the assay using elevated hybridization temperatures for better discrimination of perfect duplex from single and double mismatches. After optimization of the protocol, we demonstrated feasibility of our assay by detecting target miRNA in real total RNA samples isolated from human cancer cells.

Solvent-Dependent Formation of Os(0) Complexes by Electrochemical Reduction of [Os(CO)(2,2′-bipyridine)(L)Cl2]; L = Cl–, PrCN

Cyclic voltammetry and ultraviolet-visible/infrared (UV-vis/IR) spectroelectrochemistry were used to study the cathodic electrochemical behavior of the osmium complexes mer-[Os(III)(CO) (bpy)Cl3] (bpy = 2,2'-bipyridine) and trans(Cl)-[Os(II)(CO) (PrCN)(bpy)Cl2] at variable temperature in different solvents (tetrahydrofuran (THF), butyronitrile (PrCN), acetonitrile (MeCN)) and electrolytes (Bu4NPF6, Bu4NCl). The precursors can be reduced to mer-[Os(II)(CO) (bpy(•-))Cl3](2-) and trans(Cl)-[Os(II)(CO)(PrCN) (bpy(•-))Cl2](-), respectively, which react rapidly at room temperature, losing the chloride ligands and forming Os(0) species. mer-[Os(III)(CO) (bpy)Cl3] is reduced in THF to give ultimately an Os-Os-bonded polymer, probably [Os(0)(CO) (THF)(bpy)]n, whereas in PrCN the well-soluble, probably mononuclear [Os(0)(CO) (PrCN)(bpy)], species is formed. The same products were observed for the 2 electron reduction of trans(Cl)-[Os(II)(CO)(PrCN) (bpy)Cl2] in both solvents. In MeCN, similar to THF, the [Os(0)(CO) (MeCN)(bpy)]n polymer is produced. It is noteworthy that the bpy ligand in mononuclear [Os(0)(CO) (PrCN)(bpy)] is reduced to the corresponding radical anion at a significantly less negative potential than it is in polymeric [Os(0)(CO) (THF)(bpy)]n: ΔE1/2 = 0.67 V. Major differences also exist in the IR spectra of the Os(0) species: the polymer shows a broad ν(CO) band at much smaller wavenumbers compared to the soluble Os(0) monomer that exhibits a characteristic ν(Pr-CN) band below 2200 cm(-1) in addition to the intense and narrow ν(CO) absorption band. For the first time, in this work the M(0)-bpy (M = Ru, Os) mono- and dicarbonyl species soluble in PrCN have been formulated as a mononuclear complex. Density functional theory (DFT) and time-dependent-DFT calculations confirm the Os(0) oxidation state and suggest that [Os(0)(CO) (PrCN)(bpy)] is a square planar moiety. The reversible bpy-based reduction of [Os(0)(CO) (PrCN)(bpy)] triggers catalytic reduction of CO2 to CO and HCOO(-).

POP–Pincer Ruthenium Complexes: d6 Counterparts of Osmium d4 Species

A wide range of ruthenium complexes stabilized by the POP-pincer ligand xant(P(i)Pr2)2 (9,9-dimethyl-4,5-bis(diisopropylphosphino)xanthene) were prepared starting from cis-RuCl2{κ-S-(DMSO)4} (1; DMSO = dimethyl sulfoxide). Treatment of toluene solutions of this adduct with the diphosphine under reflux leads to RuCl2{xant(P(i)Pr2)2}(κ-S-DMSO) (2), which reacts with H2 in the presence of a Brønsted base. The reaction in the presence of Et3N affords RuHCl{xant(P(i)Pr2)2}(κ-S-DMSO) (3), whereas NaH removes both chloride ligands to give RuH2{xant(P(i)Pr2)2}(κ-S-DMSO) (4). The stirring of 3 in 2-propanol under 3 atm of H2 for a long time produces the elimination of DMSO and the coordination of H2 to yield the dihydrogen derivative, RuHCl(η(2)-H2){xant(P(i)Pr2)2} (5). In contrast to H2, PPh3 easily displaces DMSO from the metal center of 3 to afford RuHCl{xant(P(i)Pr2)2}(PPh3) (6), which can be also obtained starting from RuHCl(PPh3)3 (7) and xant(P(i)Pr2)2. In contrast to 3, complex 4 does not undergo DMSO elimination to give RuH2(η(2)-H2){xant(P(i)Pr2)2} (8) under a H2 atmosphere. However, the latter can be prepared by hydrogenation of Ru(COD)(COT) (9; COD = 1,5-cyclooctadiene and COT = 1,3,5-cyclooctatriene) in the presence of xant(P(i)Pr2)2. A more efficient procedure to obtain 8 involves the sequential hydrogenation with ammonia borane of the allenylidene derivative RuCl2(═C═C═CPh2){xant(P(i)Pr2)2} (10), which is formed from the reaction of 2 with 1,1-diphenyl-2-propyn-1-ol. The hydrogenation initially gives RuCl2(═C═CHCHPh2){xant(P(i)Pr2)2} (11), which undergoes the subsequent reduction of the Ru-C double bond to yield the hydride-tetrahydroborate complex, RuH(η(2)-H2BH2){xant(P(i)Pr2)2} (12). The osmium complex, OsCl2{xant(P(i)Pr2)2}(κ-S-DMSO) (13), reacts with 1,1-diphenyl-2-propyn-1-ol in a similar manner to its ruthenium counterpart 2 to yield the allenylidene derivative, OsCl2(═C═C═CPh2){xant(P(i)Pr2)2} (14). Ammonia borane also reduces the Cβ-Cγ double bond of the allenylidene of 14. However, the resulting vinylidene species, OsCl2(═C═CHCHPh2){xant(P(i)Pr2)2} (15), is inert. Complex 12 is an efficient catalyst precursor for the hydrogen transfer from 2-propanol to ketones, the α-alkylations of phenylacetonitrile and acetophenone with alcohols, and the regio- and stereoselective head-to-head (Z) dimerization of terminal alkynes.

Biocathodes for Enzymatic Biofuel Cells Using Laccase and Different Redox Mediators Entrapped in Polypyrrole Matrix

This paper describes a comparative study of laccase-based biocathodes containing different redox mediator species, namely porphyrin, ferrocene, osmium, and ruthenium complexes were immobilized onto carbon platforms entrapped in an electropolymerized polypyrrole matrix. Ferrocenium hexafluorophosphate (Fc), an Iron (III) porphyrin (FeTMPyP), a ruthenium complex [Ru(byp)2Cl2], and an osmium complex [Os(byp)2Cl2] were employed as redox mediators and have been characterized by cyclic voltammetry. Methanol/O2 biofuel cell tests employing the biocathodes showed that they provide higher output power as compared with other systems. In the best conditions, the maximum power densities reached values around 81 ± 4 and 71 ± 3 μW cm−2 for [Ru(bpy)2Cl2] and [Os(bpy)2Cl2] at pH 4.5, respectively.

Oxidation of hydrocarbons with H2O2/O2catalyzed by osmium complexes containing p-cymene ligands in acetonitrile

Osmium π-complexes containingp-cymene ligands efficiently catalyze (TONs up to 200 000) the oxidation of alkanes to alkyl hydroperoxides with H2O2.

A multinuclear1H,13C and11B solid-state MAS NMR study of 16- and 18-electron organometallic ruthenium and osmium carborane complexes

The first (1)H, (13)C, (31)P and (11)B solid state MAS NMR studies of electron-deficient carborane-containing ruthenium and osmium complexes [Ru/Os(p-cym)(1,2-dicarba-closo-dodecaborane-1,2-dithiolate)] are reported. The MAS NMR data from these 16-electron complexes are compared to those of free carborane-ligand and an 18-electron triphenylphosphine ruthenium adduct, and reveal clear spectral differences between 16- and 18-electron organometallic carborane systems in the solid state.

Stable tetramethyl-1,10-phenanthroline osmium(iii) complex in neutral pH as a photoluminescence-following electron-transfer reagent for the detection of acetaminophen in urine and pharmaceutical formulations

A stable [Os(tmphen)3]3+reagent was prepared in neutral aqueous solution by oxidation of [Os(tmphen)3]2+with lead(iv) oxide.

Ruthenium, osmium and rhodium complexes of 1,4-diaryl 1,4-diazabutadiene: radical versus non-radical states.

Ruthenium, osmium and rhodium complexes of 1,4-di(3-nitrophenyl)-1,4-diazabutadiene (LDAB) of types trans-[RuII(LDAB)(PPh3)2Cl2] (1), trans-[OsII(LDAB)(PPh3)2Br2] (2) and trans-[Rh(LDAB)(PPh3)2Cl2] (3) are isolated and characterized by elemental analyses, IR, mass and 1H NMR spectra including the single crystal X-ray structure determination of 1·2toluene. The α-diimine fragment of the LDAB ligand in 1·2toluene is deformed, showing a relatively longer -C=N- bond, 1.320 Å, and a shorter =CH–CH= bond, 1.395 Å. Density functional theory (DFT) calculations on trans-[Ru(LDAB)(PMe3)2Cl2] (1Me) and trans-[Os(LDAB)(PMe3)2Br2] (2Me) with singlet spin states authenticated that the closed shell singlet state (CSS) solutions of 1 and 2 are stable and no perturbation occurs because of the diradical open shell singlet (OSS) state. The EPR spectra of 3 and the Mulliken spin density distribution obtained from the DFT calculation on trans-[Rh(LDAB)(PMe3)2Cl2] (3Me) imply that the ground electronic state of 3 can be defined by the [RhIII(LDAB˙−)(PPh3)2Cl2] (3RhL˙) ↔ [RhII(LDAB)(PPh3)2Cl2] (3Rh˙L) resonating states. In solid, the contribution of 3RhL˙ is higher and the gav is 2.018 with Δg = 0.10, whereas in frozen glasses the contribution of 3Rh˙L is higher and the gav is 2.026 with Δg (frozen glasses) = 0.13. The g parameters of the electrogenerated [1]+ (g1 = 2.456, g2 = 2.128 and g3 = 1.624, Δg = 0.824), [2]+ (g1 = 2.599, g2 = 2.041 and g3 = 1.965, Δg = 0.634), [1]− (g1 = 2.138, g2 = 2.109, g3 = 1.978 and Δg = 0.160) and [2]− (g1 = 2.168, g2 = 2.097, g3 = 1.987 and Δg = 0.181) ions and the spin density distributions obtained from the DFT calculations on [1Me]+, [2Me]+, [1Me]− and [2Me]− reveal that the reversible anodic peaks of 1 and 2 at 0.11 and 0.34 V, referenced versus Fc+/Fc couple, are due to the M(III)/M(II) redox couple, while the reversible cathodic waves at −1.27 V and −0.82 V of 1 and 2 are caused by the LDAB/LDAB˙− redox couple. Both [MII(LDAB˙−)(PPh3)2Br2]− and [MI(LDAB)(PPh3)2Br2]− tautomers contribute to the ground electronic states of [1]− (g = 2.075) and [2]− (g = 2.084) ions, which are isoelectronic to 3. Time dependent (TD) DFT calculations and spectroelectrochemical measurements elucidated that lower energy absorption bands of 1 and 2 are caused by the metal to ligand charge transfer (MLCT) that disappears upon oxidation or reduction.

Dinuclear osmium(II) probes for high-resolution visualisation of cellular DNA structure using electron microscopy.

Two dinuclear osmium polypyridyl complexes function as convenient, easy to handle TEM contrast agents and facilitate the high-resolution visualisation of intracellular structure, particularly sub-nuclear detail.

Ruthenium and osmium complexes of hemilabile chiral monophosphinite ligands derived from 1D-pinitol or 1D-chiro-inositol as catalysts for asymmetric hydrogenation reactions

The monophosphinite ligands, 1D-1,2;5,6-di-O-cyclopentylidene-3-O-methyl-4-O-diphenylphosphino-chiro-inositol (D-P1), 1D-1,2;5,6-di-O-isopropylidene-3-O-methyl-4-O-diphenylphosphino-chiro-inositol (D-P2), 1D-1,2;5,6-di-O-cyclohexylidene-3-O-methyl-4-O-diphenylphosphino-chiro-inositol (D-P3), and 1D-1,2;5,6-di-O-cyclopentylidene-3-O-ethyl-4-O-diphenylphosphino-chiro-inositol (D-P4), can be conveniently prepared from the chiral natural products 1D-pinitol or 1D-chiro-inositol. On treatment of toluene solutions of RuCl2(PPh3)3 with two mole equivalents of the ligands D-PY (Y = 1-4) the complexes RuCl2(D-P1)2 (1), RuCl2(D-P2)2 (4), RuCl2(D-P3)2 (5), or RuCl2(D-P4)2 (6), respectively, are formed. Similarly, treatment of OsCl2(PPh3)3 with D-P1 gives OsCl2(D-P1)2 (7). The single crystal X-ray structure determination of 1 reveals that each D-P1 ligand coordinates to ruthenium through phosphorus and the oxygen atom of the methoxyl group. Treatment of 1 with excess LiBr or LiI results in metathesis of the chloride ligands and RuBr2(D-P1)2 (2) or RuI2(D-P1)2 (3), respectively, are formed. Exposure of a solution of 1 to carbon monoxide results in the very rapid formation of RuCl2(CO)2(D-P1)2 (8), thereby demonstrating the ease with which the oxygen donors are displaced from the metal and hence the hemilabile nature of the two bidentate D-P1 ligands in 1. Preliminary studies indicate that 1-7 act as catalysts for the asymmetric hydrogenation reactions of acetophenone and 3-quinuclidinone to give the corresponding alcohols in generally high conversions but low enantiomeric excesses.