Ten new ruthenium compounds based on the N,N,N,N-chelate Me2bpbMe2 (bpb = 1,2-bis(pyridine-2-carboximido)benzene) have prepared and characterized by 1H NMR and IR spectroscopy. The monocarbonyl compound (Me2bpbMe2)Ru(CO)(H2O) compound was generated from the reaction of the free base Me2bpbMe2H2 with Ru3(CO)12 in refluxing DMF. Isoamyl nitrite reacts with this compound to yield the trans-addition nitrosyl alkoxide (Me2bpbMe2)Ru(NO)(O-i-C5H11). Nitrosothiols similarly add in a formal trans-addition manner to yield (Me2bpbMe2)Ru(NO)(SR/Ar) (SR/Ar = S-i-C5H11, SPh, SC6F4H, SC(Me)2CHNHC(O)Me) derivatives. The (Me2bpbMe2)Ru(NO)(O-i-C5H11) compound undergoes alkoxide exchange reactions with PhOH and HOC6F4H to generate (Me2bpbMe2)Ru(NO)(OPh) and (Me2bpbMe2)Ru(NO)(OC6F4H), respectively. The neutral alkoxide/aryloxide nitrosyl compounds exhibit higher NO bands (1809–1842 cm-1) relative to their thiolate analogues (1755–1823 cm-1). The X-ray crystal structures of (Me2bpbMe2)Ru(NO)(OPh), (Me2bpbMe2)Ru(NO)(OC6F4H), and (Me2bpbMe2)Ru(NO)(SPh), have been determined, and reveal linear axial (O)N–Ru–O/S linkages consistent with trans positioning of the NO and aryloxide and -thiolate groups, and near-linear Ru–N–O moieties (164–174°) consistent with these complexes being formulated as {RuNO}6 species. The electrooxidation behavior of (Me2bpbMe2)Ru(NO)(OC6F4H), (Me2bpbMe2)Ru(NO)(SC6F4H), and (Me2bpbMe2)Ru(NO)(SPh) were examined by cyclic voltammetry and IR spectroelectrochemistry in CH2Cl2. (Me2bpbMe2)Ru(NO)(OC6F4H) and (Me2bpbMe2)Ru(NO)(SC6F4H) display reversible first oxidations, whereas (Me2bpbMe2)Ru(NO)(SPh) displays an irreversible first oxidation with likely loss of the thiolate ligand. Chemical reactivity of (Me2bpbMe2)Ru(NO)(SPh) with H+ and Me+ results in the generation of the free thiol PhSH and thioether PhSMe, respectively.
more »
« less
Electrodeposition of Ru onto Ru and Au Seed Layers from Solutions of Ruthenium Nitrosyl Sulfate and Ruthenium Chloride
The electrodeposition of Ru was investigated from solutions of ruthenium(III) nitrosyl sulfate and ruthenium(III) chloride onto seed layers of epitaxial and polycrystalline Ru and epitaxial Au. Using both galvanostatic and potentiostatic deposition modes, metallic Ru was found to electrodeposit as a porous layer comprised of (0001) oriented Ru crystallites, the presence of which was discovered and confirmed by X-ray and scanning transmission and transmission electron microscope (S/TEM) analyses. This finding was independent of the Ru salt and seed layer used. Using X-ray reflectivity (XRR), the average film density ρ e f f of the porous electrodeposited Ru layer was measured as less than the density of bulk Ru ρ R u , b u l k (14.414 g cm −3 ). Increasing the magnitude of the applied current density from −100 μ A cm −2 to −10 mA cm −2 in solutions of Ru nitrosyl sulfate increased the ρ e f f from 7.4 g cm −3 to 9.7 g cm −2 while the current efficiency decreased from 9.4% to 4.3%.
more »
« less
- Award ID(s):
- 1740270
- PAR ID:
- 10357339
- Date Published:
- Journal Name:
- Journal of The Electrochemical Society
- Volume:
- 168
- Issue:
- 5
- ISSN:
- 0013-4651
- Page Range / eLocation ID:
- 052504
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
More Like this
-
-
Epitaxial electrodeposition of Co, Cu and Ru is compared and contrasted. The seed layer for electrodeposition of all three metals was an epitaxial Ru(0001) film that was deposited at an elevated temperature onto a sapphire(0001) substrate and annealed post deposition. The epitaxial orientation relationship of the electrodeposited film and the seed layer, the epitaxial misfit strain, the role of symmetry of the seed layer versus the electrodepositing layer is addressed. In addition, the impact of underpotential deposition on film nucleation, and the growth morphology of the films is discussed. It is shown that epitaxial electrodeposition of metallic films to thicknesses of tens of nanometers is readily achievable. This paper 1189 was presented during the 241st Meeting of the Electrochemical Society, May 29–June 2, 2022.more » « less
-
Hydrogen evolution reaction catalyzed by ruthenium ion-complexed graphitic carbon nitride nanosheetsThe development of cost-effective, high-performance electrocatalysts for hydrogen evolution reaction (HER) is urgently needed. In the present study, a new type of HER catalyst was developed where ruthenium ions were embedded into the molecular skeletons of graphitic carbon nitride (C 3 N 4 ) nanosheets of 2.0 ± 0.4 nm in thickness by refluxing C 3 N 4 and RuCl 3 in water. This took advantage of the strong affinity of ruthenium ions to pyridinic nitrogen of the tri- s -triazine units of C 3 N 4 . The formation of C 3 N 4 –Ru nanocomposites was confirmed by optical and X-ray photoelectron spectroscopic measurements, which suggested charge transfer from the C 3 N 4 scaffold to the ruthenium centers. Significantly, the hybrid materials were readily dispersible in water and exhibited apparent electrocatalytic activity towards HER in acid and their activity increased with the loading of ruthenium metal centers in the C 3 N 4 matrix. Within the present experimental context, the sample saturated with ruthenium ion complexation at a ruthenium to pyridinic nitrogen atomic ratio of ca. 1 : 2 displayed the best performance, with an overpotential of only 140 mV to achieve the current density of 10 mA cm −2 , a low Tafel slope of 57 mV dec −1 , and a large exchange current density of 0.072 mA cm −2 . The activity was markedly lower when C 3 N 4 was embedded with other metal ions such as Fe 3+ , Co 3+ , Ni 3+ and Cu 2+ . This suggests minimal contributions from the C 3 N 4 nanosheets to the HER activity, and the activity was most likely due to the formation of Ru–N moieties where the synergistic interactions between the carbon nitride and ruthenium metal centers facilitated the adsorption of hydrogen. This was strongly supported by results from density functional theory calculations.more » « less
-
The synthesis, characterization, and redox behavior of aryloxide complexes containing an increasing number of internal hydrogen bonds (OEP)Ru(NO)(OArxH) (OEP = octaethylporphyrinato dianion; x = 0, 1, 2) are reported. These nitrosyl aryloxide compounds were characterized by X‐ray crystallography, IR and 1H NMR spectroscopy. The IR spectra displayed uNO frequencies in the 1823–1843 cm‐1 range with compounds possessing more internal hydrogen bonds demonstrating higher uNO frequencies due to diminished π‐backdonation to the Ru‐NO fragment. Comparison of the distinct uNH and δN‐H signals in the IR and 1H NMR spectra of the free and complexed OAr1H/OAr2H ligands support the notion of additional electron density being removed via intramolecular hydrogen bonding. Results of DFT calculations on the (porphine)Ru(NO)(OArxH) models (porphine = unsubstituted porphyrin) reveal that the HOMOs of these complexes have significant axial ligand contributions, whereas the HOMOs of the five‐coordinate [(porphine)RuNO)]+ cation resides mostly on the equatorial porphyrin macrocycle. The electrochemical results of these (OEP)Ru(NO)(OArxH) complexes in CH2Cl2 reveal first oxidations that occur at increasingly positive potentials when more internal hydrogen bonds are present. Based on the DFT and preliminary IR spectroelectrochemical results, we propose that the electrooxidations result in eventual dissociation of the axial aryloxide ligands.more » « less
-
The coupling of carbon dioxide and ethylene to generate value added chemicals has been part of recent fundamental advances to improve sustainability in commercial chemical synthons. A formal zerovalent triphosphine ligated ruthenium complex, (tBuP(CH2CH2PEt2)2)Ru(κ-S-DMSO)(C2H4), was found to promote CO2 activation, affording products derived from both a 1:1 and 1:2 ethylene to CO2 coupling stoichiometry. The equimolecular coupling reaction selectively afforded a five-membered ruthenium lactone species, (tBuP(CH2CH2PEt2)2)Ru(κ-S-DMSO)(κ-C,κ-O-CH2CH2CO2), under low CO2 pressure. At higher CO2 pressure, the ruthenium lactone complex activated a second equivalent of CO2, yielding a dimeric methylmalonate ruthenium compound, [(tBuP(CH2CH2PEt2)2)Ru(μ2, κ1-O, κ2-O,O-O2CCHCH3CO2)]2. Both carbon dioxide activation products were characterized by X-ray diffraction. Preliminary mechanistic studies suggest that reversible β-H elimination is a key process in conversion between the two ruthenium carboxylate species. A rare formally zerovalent ruthenium coordination compound stabilized only by ethylene and DMSO ligands was also isolated and characterized.more » « less
An official website of the United States government

