A Zeolite‐Supported Molecular Ruthenium Complex with η6‐C6H6 Ligands: Chemistry Elucidated by Using Spectroscopy and Density Functional Theory

An essentially molecular ruthenium–benzene complex anchored at the aluminum sites of dealuminated zeolite Y was formed by treating a zeolite‐supported mononuclear ruthenium complex, [Ru(acac)(η²‐C₂H₄)₂]⁺ (acac=acetylacetonate, C₅H₇O₂^?), with ¹³C₆H₆ at 413 K. IR, ¹³C NMR, and extended X‐ray absorption fine structure (EXAFS) spectra of the sample reveal the replacement of two ethene ligands and one acac ligand in the original complex with one ¹³C₆H₆ ligand and the formation of adsorbed protonated acac (Hacac). The EXAFS results indicate that the supported [Ru(η⁶‐C₆H₆)]²⁺ incorporates an oxygen atom of the support to balance the charge, being bonded to the zeolite through three Ru? O bonds. The supported ruthenium–benzene complex is analogous to complexes with polyoxometalate ligands, consistent with the high structural uniformity of the zeolite‐supported species, which led to good agreement between the spectra and calculations at the density functional theory level. The calculations show that the interaction of the zeolite with the Hacac formed on treatment of the original complex with ¹³C₆H₆ drives the reaction to form the ruthenium–benzene complex.     

Characterization of oxide supported metal carbonyl clusters

The chemisorption of [Ma₃(CO)_{1 2}] on silica (M = Ru and Os) and alumina (M = Os) has been studied by vibrational and X-ray absorption spectroscopies making close comparisons with model compounds. The results indicate that the first chemisorption species observed has the form [M₃H(CO)₁₀(O---O)]; the bridging hydride was observed directly for the silica systems as evidenced by the M-H-M bending vibration in the i.r. Also consistent with this structure are the EXAFS analysis of the Ru/SiOz material. This indicated an essentially equilateral ruthenium triangle and coordination to oxygen. The published low frequency Raman data on the Os/Al2Oa product was shown to match most closely with that of model compounds with a bidentate oxygen donor ligand (acac or O2CR). The tethered cluster [O_s3H₂(CO)₉(PPh₂C₂H₄SIL)] was found to be a relatively short lived species on a silica surface. Under ambient conditions it reacts further and the i.r., EXAFS and ³¹P NMR data of this species suggest that the two osmium atoms not coordinated to the tethering phosphine become involved with a bidentate site from the surface.     

Molecular chemistry in a zeolite: genesis of a zeolite Y-supported ruthenium complex catalyst

Dealuminated zeolite Y was used as a crystalline support for a mononuclear ruthenium complex synthesized from cis-Ru(acac)2(C2H4)2. Infrared (IR) and extended X-ray absorption fine structure spectra indicated that the surface species were mononuclear ruthenium complexes, Ru(acac)(C2H4)2(2+), tightly bonded to the surface by two Ru-O bonds at Al(3+) sites of the zeolite. The maximum loading of the anchored ruthenium complexes was one complex per two Al(3+) sites; at higher loadings, some of the cis-Ru(acac)2(C2H4)2 was physisorbed. In the presence of ethylene and H2, the surface-bound species entered into a catalytic cycle for ethylene dimerization and operated stably. IR data showed that at the start of the catalytic reaction, the acac ligand of the Ru(acac)(C2H4)2(2+) species was dissociated and captured by an Al(3+) site. Ethylene dimerization proceeded approximately 600 times faster with a cofeed of ethylene and H2 than without H2. These results provide evidence of the importance of the cooperation of the Al(3+) sites in the zeolite and the H2 in the feed for the genesis of the catalytically active species. The results presented here demonstrate the usefulness of dealuminated zeolite Y as a nearly uniform support that allows precise synthesis of supported catalysts and detailed elucidation of their structures.     

Single‐Site Zeolite‐Anchored Organoiridium Carbonyl Complexes: Characterization of Structure and Reactivity by Spectroscopy and Computational Chemistry

A family of HY zeolite‐supported cationic organoiridium carbonyl complexes was formed by reaction of Ir(CO)₂(acac) (acac=acetylacetonate) to form supported Ir(CO)₂ complexes, which were treated at 298 K and 1 atm with flowing gas‐phase reactants, including C₂H₄, H₂, ¹²CO, ¹³CO, and D₂O. Mass spectrometry was used to identify effluent gases, and infrared and X‐ray absorption spectroscopies were used to characterize the supported species, with the results bolstered by DFT calculations. Because the support is crystalline and presents a nearly uniform array of bonding sites for the iridium species, these were characterized by a high degree of uniformity, which allowed a precise determination of the species involved in the replacement, for example, of one CO ligand of each Ir(CO)₂ complex with ethylene. The supported species include the following: Ir(CO)₂, Ir(CO)(C₂H₄)₂, Ir(CO)(C₂H₄), Ir(CO)(C₂H₅), and (tentatively) Ir(CO)(H). The data determine a reaction network involving all of these species.     

The trans influence of the pyridine ligand on ruthenium(II)–porphyrin–carbene complexes

In the two ruthenium(II)–porphyrin–carbene complexes ­(di­benzoyl­carbenyl‐κC)(pyridine‐κN)(5,10,15,20‐tetra‐p‐tolyl­porphyrinato‐κ⁴N)­ruthenium(II), [Ru(C₁₅H₁₀O₂)(C₅H₅N)(C₄₈H₃₆N₄)], (I), and (pyridine‐κN)(5,10,15,20‐tetra‐p‐tolyl­porphyrinato‐κ⁴N)[bis(3‐tri­fluoro­methyl­phenyl)­carbenyl‐κC]­ruthenium(II), [Ru(C₁₅H₈F₆)(C₅H₅N)(C₄₈H₃₆N₄)], (II), the pyridine ligand coordinates to the octahedral Ru atom trans with respect to the carbene ligand. The C(carbene)—Ru—N(pyridine) bonds in (I) coincide with a crystallographic twofold axis. The Ru—C bond lengths of 1.877 (8) and 1.868 (3) Å in (I) and (II), respectively, are slightly longer than those of other ruthenium(II)–porphyrin–carbene complexes, owing to the trans influence of the pyridine ligands.     

Five-Membered Ruthenacycles: Ligand-Assisted Alkyne Insertion into 1,3-N,S-Chelated Ruthenium Borate Species

Building upon previous work, the chemistry of [(η⁶-p-cymene)Ru{P(OMe)₂OR}Cl₂], (R=H or Me) has been extended with [H₂B(mbz)₂]⁻ (mbz=2-mercaptobenzothiazolyl) using different Ru precursors and borate ligands. As a result, a series of 1,3-N,S-chelated ruthenium borate complexes, for example, [(κ²-N,S-L)PR₃Ru{κ³-H,S,S’−H₂B(L)₂}], ( 2 a – d and 2 a’ – d’ ; R=Ph, Cy, OMe or OPh and L=C₅H₄NS or C₇H₄NS₂) and [Ru{κ³-H,S,S’-H₂B(L)₂}₂], ( 3 : L=C₅H₄NS, 3’ : L=C₇H₄NS₂) were isolated upon treatment of [(η⁶-p-cymene)RuCl₂PR₃], 1 a – d (R=Ph, Cy, OMe or OPh) with [H₂B(mp)₂]⁻ or [H₂B(mbz)₂]⁻ ligands (mp=2-mercaptopyridyl). All the Ru borate complexes, 2 a – d and 2 a’ – d’ are stabilized by phosphine/phosphite and hemilabile N,S-chelating ligands. Treatment of these Ru borate species, 2 a’ – c’ with various terminal alkynes yielded two different types of five-membered ruthenacycle species, namely [PR₃{C₇H₄S₂-(E)-N-C=CH(R ’ )}Ru{κ³-H,S,S ’ −H₂B(L)₂}], ( 4 – 4’ ; R=Ph and R ’ =CO₂Me or C₆H₄NO₂; L=C₇H₄NS₂) and [PR₃{C₇H₄NS-(E)-S-C=CH(R ’ )}Ru{κ³-H,S,S ’ −H₂B(L)₂}], ( 5 – 5’ , 6 and 7 ; R=Ph, Cy or OMe and R ’ =CO₂Me or C₆H₄NO₂; L=C₇H₄NS₂). All these five-membered ruthenacycle species contain an exocyclic C=C moiety, presumably formed by the insertion of a terminal alkyne into the Ru−N and Ru−S bonds. The new species have been characterized spectroscopically and the structures were further confirmed by single-crystal X-ray diffraction analysis. Theoretical studies and chemical-bonding analyses established that charge transfer occurs from phosphorus to ruthenium center following the trend PCy₃<PPh₃<P(OPh)₃<P(OMe)₃.     

A site-isolated rhodium-diethylene complex supported on highly dealuminated Y zeolite: synthesis and characterization

The reaction of Rh(C2H4)2(acac) with the partially dehydroxylated surface of dealuminated zeolite Y (calcined at 773 K) and treatments of the resultant surface species in various atmospheres (He, CO, H2, and D2) were investigated with infrared (IR), extended X-ray absorption fine structure (EXAFS), and 13C NMR spectroscopies. The IR spectra show that Rh(C2H4)2(acac) reacted readily with surface OH groups of the zeolite, leading to loss of acac ligands from the Rh(C2H4)2(acac) and formation of supported mononuclear rhodium complexes, confirmed by the lack of Rh-Rh contributions in the EXAFS spectra; each Rh atom was bonded on average to two oxygen atoms of the zeolite surface with a Rh-O distance of 2.19 A. IR, EXAFS, and 13C NMR spectra show that the ethylene ligands remained bonded to the Rh center in the supported complex. Treatment of the sample in CO led to the formation of site-isolated Rh(CO)2 complexes bonded to the zeolite. The sharpness of the nu(CO) bands in the IR spectrum gives evidence of a nearly uniform supported Rh(CO)2 complex and, by inference, the near uniformity of the mononuclear rhodium complex with ethylene ligands from which it was formed. The supported complex with ethylene ligands reacted with H2 to give ethane, and it also catalyzed ethylene hydrogenation at 294 K.     

Oxide- and zeolite-supported isostructural ir(c(2)h(4))(2) complexes: molecular-level observations of electronic effects of supports as ligands

Zeolite Hβ- and γ-Al(2)O(3)-supported mononuclear iridium complexes were synthesized by the reaction of Ir(C(2)H(4))(2)(acac) (acac is acetylacetonate) with each of the supports. The characterization of the surface species by extended X-ray absorption fine structure (EXAFS) and infrared (IR) spectroscopies demonstrated the removal of acac ligands during chemisorption, leading to the formation of essentially isostructural Ir(C(2)H(4))(2) complexes anchored to each support by two Ir-O(support) bonds. Atomic-resolution aberration-corrected scanning transmission electron microscopy (STEM) images confirm the spectra, showing only isolated Ir atoms on the supports with no evidence of iridium clusters. These samples, together with previously reported Ir(C(2)H(4))(2) complexes on zeolite HY, zeolite HSSZ-53, and MgO supports, constitute a family of isostructural supported iridium complexes. Treatment with CO led to the replacement of the ethylene ligands on iridium with CO ligands, and the ν(CO) frequencies of these complexes and white line intensities in the X-ray absorption spectra at the Ir L(III) edge show that the electron density on iridium increases in the following order on these supports: zeolite HY < zeolite Hβ < zeolite HSSZ-53 ? γ-Al(2)O(3) < MgO. The IR spectra of the iridium carbonyl complexes treated in flowing C(2)H(4) show that the CO ligands were replaced by C(2)H(4), with the average number of C(2)H(4) groups per Ir atom increasing as the amount of iridium was increasingly electron-deficient. In contrast to the typical supported catalysts incorporating metal clusters or particles that are highly nonuniform, the samples reported here, incorporating uniform isostructural iridium complexes, provide unprecedented opportunities for a molecular-level understanding of how supports affect the electronic properties, reactivities, and catalytic properties of supported metal species.     

Structure and catalytic activity of the ruthenium(I) sawhorse‐type complex [Ru2{μ,η2‐CF3(CF2)5COO}2(DMSO)2(CO)4]

The title compound, cis‐di‐μ‐perfluoroheptanoato‐κ⁴O:O′‐bis[dicarbonyl(dimethyl sulfoxide‐κS)ruthenium(I)](Ru—Ru), [Ru₂(C₇F₁₃O₂)₂(C₂H₆OS)₂(CO)₄], is a sawhorse‐type dinuclear ruthenium complex with two bridging perfluoroheptanoate ligands, and with two dimethyl sulfoxide (DMSO) ligands in the axial positions coordinating via the S atoms. It is a new example of a compound with an aliphatic fluorinated carboxylate ligand. The Ru—Ru bond distance of 2.6908 (3) Å indicates a direct Ru—Ru interaction. The compound is an active catalyst in transvinylation of propionic acid with vinyl acetate.     

Application of a Structure/Oxidation‐State Correlation to Complexes of Bridging Azo Ligands

Based on data from more than 40 crystal structures of metal complexes with azo‐based bridging ligands (2,2′‐azobispyridine, 2,2′‐azobis(5‐chloropyrimidine), azodicarbonyl derivatives), a correlation between the N? N bond lengths (d_NN) and the oxidation state of the ligand (neutral, neutral/back‐donating, radical‐anionic, dianionic) was derived. This correlation was applied to the analysis of four ruthenium compounds of 2,2′‐azobispyridine (abpy), that is, the new asymmetrical rac‐[(acac)₂Ru1(μ‐abpy)Ru2(bpy)₂](ClO₄)₂ ([ 1 ](ClO₄)₂), [Ru(acac)₂(abpy)] ( 2 ), [Ru(bpy)₂(abpy)](ClO₄)₂ ([ 3 ](ClO₄)₂), and meso‐[(bpy)₂Ru(μ‐abpy)Ru(bpy)₂](ClO₄)₃ ([ 4 ](ClO₄)₃; acac^?=2,4‐pentanedionato, bpy=2,2′‐bipyridine). In agreement with DFT calculations, both mononuclear species 2 and 3 ²⁺ can be described as ruthenium(II) complexes of unreduced abpy⁰, with 1.295(5)<d_NN<1.320(3) Å, thereby exhibiting effects from π back‐donation. However, the abpy ligand in both the asymmetrical diamagnetic compound 1 ²⁺ (d_NN=1.374(6) Å) and the symmetrical compound 4 ³⁺ (d_NN=1.360(7), 1.368(8) Å) must be formulated as abpy^.?. Remarkably, the addition of [Ru^II(bpy)₂]²⁺ to mononuclear [Ru^II(acac)₂(abpy⁰)] induces intracomplex electron‐transfer under participation of the noninnocent abpy bridge to yield rac‐[(acac)₂Ru1^III(μ‐abpy^.?)Ru2^II(bpy)₂]²⁺ ( 1 ²⁺) with strong antiferromagnetic coupling between abpy^.? and Ru^III (DFT (B3LYP/LANL2DZ/6‐31G*)‐calculated triplet–singlet energy separation E_S=1?E_S=0=11739 cm^?1). Stepwise one‐electron transfer was studied for compound 1 ⁿ, n=1?, 0, 1+, 2+, 3+, by UV/Vis/NIR spectroelectrochemistry, EPR spectroscopy, and by DFT calculations. Whereas the first oxidation of compound 1 ²⁺ was found to mainly involve the central ligand to produce an (abpy⁰)‐bridged Class I mixed‐valent Ru1^IIIRu2^II species, the first reduction of compound 1 ²⁺ affected both the bridge and Ru1 atom to form a radical complex ( 1 ⁺), with considerable metal participation in the spin‐distribution. Further reduction moves the spin towards the {Ru2(bpy)₂} entity.     

Multiple Coordination of Metal Atoms to Arenes: The Coordination of Six Ruthenium Atoms to Naphthalene-1,8-diyl in [Ru6(μ6-C10H6)(μ3-PPh)(CO)14]

Six ruthenium atoms are coordinated to the naphthalene-1,8-diyl ligand in the cluster [Ru₆(CO)₁₄(C₁₀H₆)(PPh)] through two Ru−C σ bonds, two η², and two η³ interactions (section of structure depicted on the right). The complex could, therefore, serve as a model for the chemisorption of naphthalene on a step-site on a (111) metal surface.     

Ruthenium NNN complexes with a 2‐hydroxypyridylmethylene fragment for transfer hydrogenation of ketones

Four NNN tridentate ligands L₁–L₄ containing 2‐methoxypyridylmethene or 2‐hydroxypyridylmethene fragment were synthesized and introduced to ruthenium centers. When (HOC₅H₃NCH₂C₅H₃NC₅H₇N₂) (L₂) and (HOC₅H₃NCH₂C₅H₃NC₆H₆N₃) (L₄) reacted with RuCl₂(PPh₃)₃, two ruthenium chloride products Ru(L₂)(PPh₃)Cl₂ ( 1 ) and Ru(L₄)(PPh₃)Cl₂ ( 2 ) were isolated, respectively. Reactions of (MeOC₅H₃NCH₂C₅H₃NC₅H₇N₂) (L₁) and (MeOC₅H₃NCH₂C₅H₃NC₆H₆N₃) (L₃) with RuCl₂(PPh₃)₃ in the presence of NH₄PF₆ generated two dicationic complexes [Ru(L₁)₂][PF₆]₂ ( 3 ) and [Ru(L₃)₂][PF₆]₂ ( 4 ), respectively. Complex 1 reacted with CO to afford product [Ru(L₂)(PPh₃)(CO)Cl][Cl]. The catalytic activity for transfer hydrogenation of ketones was investigated. Complex 1 showed the highest activity, with a turnover frequency value of 1.44 × 10³ h^?1 for acetophenone, while complexes 3 and 4 were not active.     

Chemistry of 2-(arylazo)phenolate complexes of ruthenium. Synthesis,structure and reactivities

A group of six ruthenium(III) complexes of type [Ru(acac)(L)₂]where acac=acetylacetonate anion and L=2-(arylazo)-4-methylphenolate anion or 1-(phenylazo)-2-naphtholate anion have been synthesized and characterized Structural characterization of a representative complex where L=1-(phenylazo)-2-naphtholate anionshows that the azophenolate ligands are coordinated as NO-donor ligands forming six-membered chelate rings The complexes are paramagnetic (low-spin d⁵S=1/2) and show rhombic ESR spectra in 1:1 dichloromethane–toluene solution at 77 K In carbon tetrachloride solution these complexes show intense LMCT transitions in the visible region together with weak ligand-field transitions in the near-IR region All the complexes display two cyclic voltammetric responses a ruthenium(III)–ruthenium(IV) oxidation in the range of 083 to 103 V vs SCE and a ruthenium(III)–ruthenium(II) reduction in the range of −024 to −052 V vs SCE Formal potentials of both the couples correlate linearly with the Hammett constant of the para substituent in the arylazo fragment of the 2-(arylazo)-4-methylphenolate ligand The ruthenimn(IV) and ruthenium(II) congeners of the [Ru^III(acac)(L)₂] complexes have been generated by chemical or electrochemical methods and they have been characterized by electronic spectroscopy and cyclic voltammetry.     

Synthesis, Crystal Structure of Ruthenium 1,2－Naphthoquinone－1－oxime Complex and Its Mediated C－－C Coupling Reactions of Ter－minal Alkynes

Substituted decarbonylation reaction of ruthenium 1,2‐naphthoquinone‐1‐oxime (1‐nqo) complex, cis‐, cis‐[Ru| ζ²‐N(O)C₁₀‐H₆O|₂(CO)₂] (1), with acetonitrile gave cis‐, cis‐[Ru | ζ²‐ N(O)C₁₀H₆O|₂(CO)(NCMe)] (2). Complex 2 was fully characterized by ¹H NMR, FAB MS, IR spectra and single crystal X‐ray analysis. Complex 2 maintains the coordination structure of 1 with the two naphthoquinonic oxygen atoms, as well as the two oximato nitrogen atoms located cis to each other, showing that there is no ligand rearrangement of the 1‐nqo ligands during the substitution reaction. The carbonyl group originally trans to the naphthoquinonic oxygen in one 1‐nqo ligand is left in its original position [O(5)‐Ru‐C(1), 174.0(6)°], while the other one originally trans to the oximato group of the other 1‐nqo ligand is substituted by NCMe [N(1)‐Ru‐N(3), 170.6(6)°]. This shows that the carbonyl trans to oximato group is more labile than the one trans to naphthoquinonic O atom towards substitution. This is probably due to the comparatively stronger ± back bonding from ruthenium metal to the carbonyl group trans to naphthoquinonic O atom, than the one trans to oximato group, resulting in the comparatively weaker Ru–‐CO bond for the latter and consequently easier replacement of this carbonyl. Selected coupling of phenylacetylene mediated by 2 gave a single trans‐dimerization product 3, while 2 mediated coupling reaction of methyl propiolate produced three products: one trans‐dimerization product 4 and two cyclotrimeric products 5 and 6.     

二氧化碳在铜表面的吸附研究及其光致分解

使用X光电子能谱(XPS)及高分辨电子能量损失谱(HREELS)研究了二氧化碳在铜表面的吸附及其光化学反应.通过实验条件控制将物理吸附及化学吸附的二氧化碳吸附物种分别分离在规整铜表面及无序铜表面上,并使用193 nm激光对其照射研究其相应的光化学反应.结果表明只有化学吸附的二氧化碳物种在光诱导下发生了解理反应,而物理吸附的二氧化碳未发生反应.     

(η6‐Hexamethylbenzene)(mesidine)­ditriflatoruthenium(II)

The crystal structure of the title complex, (η⁶‐hexamethylbenzene)bis(trifluoromethanesulfonato‐O)(2,4,6‐trimethylanil­ine‐N)ruthenium(II), [Ru(CF₃O₃S)₂(C₁₂H₁₈)(C₉H₁₃N)], is described. The complex has the classic three‐legged piano‐stool structure with a planar arene 1.667 Å from the metal, two monodentate O‐bound tri­fluoro­methane­sulfonate ligands [Ru—O 2.169 (2) and 2.174 (2) Å] and one N‐bound mesidine ligand [Ru—N 2.198 (2) Å]. The Ru—N distance is relatively long and the average Ru—O distance is relatively short when compared with previously characterized Ru^II complexes.     

Antioxidant Activity of Ruthenium Cyclopentadienyl Complexes Bearing Succinimidato and Phthalimidato Ligands

In these studies, we investigated the antioxidant activity of three ruthenium cyclopentadienyl complexes bearing different imidato ligands: (η⁵-cyclopentadienyl)Ru(CO)₂-N-methoxysuccinimidato (1), (η⁵-cyclopentadienyl)Ru(CO)₂-N-ethoxysuccinimidato (2), and (η⁵-cyclopentadienyl)Ru(CO)₂-N-phthalimidato (3). We studied the effects of ruthenium complexes 1–3 at a low concentration of 50 µM on the viability and the cell cycle of peripheral blood mononuclear cells (PBMCs) and HL-60 leukemic cells exposed to oxidative stress induced by hydrogen peroxide (H₂O₂). Moreover, we examined the influence of these complexes on DNA oxidative damage, the level of reactive oxygen species (ROS), and superoxide dismutase (SOD) activity. We have observed that ruthenium complexes 1–3 increase the viability of both normal and cancer cells decreased by H₂O₂ and also alter the HL-60 cell cycle arrested by H₂O₂ in the sub-G1 phase. In addition, we have shown that ruthenium complexes reduce the levels of ROS and oxidative DNA damage in both cell types. They also restore SOD activity reduced by H₂O₂. Our results indicate that ruthenium complexes 1–3 bearing succinimidato and phthalimidato ligands have antioxidant activity without cytotoxic effect at low concentrations. For this reason, the ruthenium complexes studied by us should be considered interesting molecules with clinical potential that require further detailed research.     

Electronic structures of heterometallic complexes [Ru(NO)(NO2)4(OH)ZnL n ] according to the data of quantum-chemical calculations and photoelectron spectroscopy

A new complex [Ru(NO)(NO₂)₄(OH)Zn(PyO)₂(H₂O)](PyO is pyridine-N-oxide) is synthesized and structurally characterized. The new complex has the face coordination of the [Ru(NO)(NO₂)₄(OH)]^2? anion to the Zn²⁺ cation similar to that in the earlier obtained complexes with other organic ligands. The methods of quantum chemistry and photoelectron spectroscopy show that the electronic structures of the [Ru(NO)(NO₂)₄(OH)ZnL _n ] heterometallic complexes depend weakly on the nature of the ligands (L = Ph₃PO, C₅H₅N, and C₅H₅N-O) coordinated to Zn²⁺ and are primarily determined by the electron density redistribution from the terminal nitro and nitroso groups of the ruthenium fragment to the zinc atom. The maximum change in the charge related to the nitroso group correlates with the strongest change in the energy of the occupied molecular orbital (HOMO-2 of the anion) oriented along the NO-Ru-OH coordinate.     

Three Bis‐BODIPY Analogous Diruthenium Redox Series: Characterization and Electronic Structure Analysis

The dianion derived from (2Z,6Z)‐3,7‐diphenyl‐N2,N6‐di(pyridin‐2‐yl)pyrrolo[2,3‐f]indole‐2,6(1H,5H)‐diimine (H₂BL), a modified BODIPY ligand precursor, is shown to be capable of bridging two metal complex fragments RuL₂, L=2,4‐pentanedionato (acac^?), 2,2’‐bipyridine (bpy) or 2‐phenylazopyridine (pap) in [Ru(acac)₂Ru(μ‐BL)Ru(acac)₂] ( 1 / 2 ), [Ru(bpy)₂Ru(μ‐BL)Ru(bpy)₂](ClO₄)₂ ([ 3 ](ClO₄)₂) and [Ru(pap)₂Ru(μ‐BL)Ru(pap)₂](ClO₄)₂ ([ 4 ](ClO₄)₂). The compounds, including a diastereoisomeric pair 1 (meso) and 2 (rac) were spectroscopically and structurally characterized. Reversible electron transfers as revealed by cyclic and differential pulse voltammetry allowed for an EPR and UV‐vis‐NIR spectroelectrochemical investigation of several neighboring charge states. Together with susceptibility measurements and TD‐DFT calculations the assignment of oxidation states reveals that 1 , 2 are diruthenium(III) species which can be oxidized or reduced by one electron whereas 3 ²⁺ and 4 ²⁺ contain ruthenium(II) and get reduced or oxidized mainly at the dianionic bridge ( 3 ²⁺) or are reduced at the ancillary ligands pap ( 4 ²⁺).     

Temperature-programmed desorption/pulse surface reaction (tpd/tpsr) studies of CH4, C2H6, C2H4, and CO over a cobalt/MWNTs catalyst

Summary Temperature-programmed desorption (TPD) of CH₄, C₂H₆, C₂H₄, and CO and temperature-programmed pulse surface reactions (TPSR) of CH₄, C₂H₆, C₂H₄, CO, and CO/H₂ over a Co/MWNTs catalyst have been investigated. The TPD results indicated that CH₄ and C₂H₆ mainly exist as physisorbed species on the Co/MWNTs catalyst surface, whilst C₂H₄ and CO exist as both physisorbed and chemisorbed species. The TPSR results indicated that CH₄ and C₂H₆ do not undergo reaction between room temperature and 450^oC. Pulsed C₂H₄ can be transformed into CH₄ at 400 ^oC whilst pulsed CO can be transformed into CO₂ at 100 or 150^oC. In gaseous mixtures of CO and H₂ containing excess CO, the products of pulsed reaction were CH₃CHO and CH₃OH. When the ratio of CO and H₂ was 1:2, pulsed CO and H₂ were transformed into CH₃CHO, CH₃OH and CH₄. In H₂ gas flow, pulsed CO was transformed into a mixture of CH₃CHO and CH₄ between 200 and 250^oC and was transformed into CH₄ only above 250^oC.