Redox Properties and Catalytic Ability toward Electrochemical Proton Reduction of Sulfur-Bridged Trinuclear Mo3S4 Complexes Containing Acetate, Trifluoroacetate, and/or Dithiophosphate as Bridging Ligands

2015 ◽  
Vol 88 (4) ◽  
pp. 565-571
Author(s):  
Keisuke Kawamoto ◽  
Akio Ichimura ◽  
Hideki Hashimoto ◽  
Isamu Kinoshita ◽  
Masakazu Hirotsu ◽  
...  
Keyword(s):  
Redox Properties ◽  
Proton Reduction ◽  
Bridging Ligands

Photochromic and Redox Properties of Bisterpyridine Ruthenium Complexes Based on Dimethyldihydropyrene Units as Bridging Ligands

2011 ◽  
Vol 50 (21) ◽  
pp. 10581-10591 ◽  
Author(s):  
Neus Vilà ◽  
Guy Royal ◽  
Frédérique Loiseau ◽  
Alain Deronzier
Keyword(s):  
Ruthenium Complexes ◽  
Redox Properties ◽  
Bridging Ligands

scholarly journals Bimetallic nickel–cobalt hydrides in H2 activation and catalytic proton reduction

2019 ◽  
Vol 10 (3) ◽  
pp. 761-767 ◽  
Author(s):  
Xiaoxiao Chu ◽  
Jihao Jin ◽  
Bangrong Ming ◽  
Maofu Pang ◽  
Xin Yu ◽  
...  
Keyword(s):  
Redox Properties ◽  
Proton Reduction ◽  
Nickel Cobalt

The synergism of the redox properties of nickel and cobalt enables bimetallic NiCo complexes to process H2.

Synthesis and redox properties of a phosphine-subsituted para-dioxolene and its bimetallic palladium complex

2008 ◽  
Vol 86 (10) ◽  
pp. 976-981 ◽  
Author(s):  
Sharon L Caldwell ◽  
Joe B Gilroy ◽  
Rajsapan Jain ◽  
Evan Crawford ◽  
Brian O Patrick ◽  
...  
Keyword(s):  
Palladium Complex ◽  
Electronic Spectroscopy ◽  
Chemical Oxidation ◽  
Redox Properties ◽  
Redox Activity ◽  
Redox Potentials ◽  
Cationic Complex ◽  
Bridging Ligands ◽  
Reduction Potentials ◽  
Bimetallic Palladium

Oxidation of 2,5-bis(diphenylphosphino)-1,4-hydroquinone (8) with iodobenzene diacetate produces the corresponding bis(phosphine) substituted benzoquinone (9), the first phosphine-substitued quinone. Cyclic voltammetry studies reveal that the redox functionality of the quinone unit in 9 is retained, and the reduction potentials render this compound slightly more easily reduced than the parent p-benzoquinone. Reaction of the precursor hydroquinone 8 with Pd(hfac)2 affords a binuclear complex 10 with the hydroquinonate ligand bridging two Pd(hfac) substrates. The redox activity of the bridging dioxolene ligand is retained in complex 10, although there are significant changes in the redox potentials relative to those of the free quinone 9. Chemical oxidation of 10 with AgPF6 yields a persistent cationic complex 11, which, based on EPR and electronic spectroscopy, can be formulated as containing a bridging semiquinone ligand.Key words: p-quinones, phosphines, bridging ligands, redox properties.

scholarly journals Influence of nitro substituents on the redox, electronic, and proton reduction catalytic behavior of phenolate-based [N2O3]-type cobalt(iii) complexes

2019 ◽  
Vol 48 (39) ◽  
pp. 14669-14677 ◽  
Author(s):  
Debashis Basu ◽  
Shivnath Mazumder ◽  
Kenneth K. Kpogo ◽  
Cláudio N. Verani
Keyword(s):  
Redox Properties ◽  
Proton Reduction ◽  
Catalytic Behavior ◽  
Cobalt Species

The electronic and redox properties of two new nitro-substituted cobalt species are investigated towards proton reduction.

Modulation of electronic and redox properties in phenolate-rich cobalt(iii) complexes and their implications for catalytic proton reduction

2015 ◽  
Vol 44 (7) ◽  
pp. 3454-3466 ◽  
Author(s):  
Debashis Basu ◽  
Marco M. Allard ◽  
Fernando R. Xavier ◽  
Mary Jane Heeg ◽  
H. Bernhard Schlegel ◽  
...  
Keyword(s):  
Catalytic Activity ◽  
Cobalt Complexes ◽  
Redox Properties ◽  
Proton Reduction

The redox, spectroscopic and catalytic activity of a series of cobalt complexes with phenolate-rich environments was investigated. The complex [CoIII(LCl)MeOH] shows considerable proton reduction in MeCN:HOAc with TON = 10.8.

Tuning the Redox Activity of Metal−Organic Frameworks for Enhanced, Selective O2 Binding

2019 ◽  
Author(s):  
Andrew Rosen ◽  
M. Rasel Mian ◽  
Timur Islamoglu ◽  
Haoyuan Chen ◽  
Omar Farha ◽  
...  
Keyword(s):  
Density Functional ◽  
Metal Organic Frameworks ◽  
Redox Activity ◽  
Screening Methods ◽  
Bridging Ligands ◽  
Metal Centers ◽  
Computational Screening ◽  
Open Metal Sites ◽  
Metal Organic ◽  
Unsaturated Metal Sites

<p>Metal−organic frameworks (MOFs) with coordinatively unsaturated metal sites are appealing as adsorbent materials due to their tunable functionality and ability to selectively bind small molecules. Through the use of computational screening methods based on periodic density functional theory, we investigate O<sub>2</sub> and N<sub>2</sub> adsorption at the coordinatively unsaturated metal sites of several MOF families. A variety of design handles are identified that can be used to modify the redox activity of the metal centers, including changing the functionalization of the linkers (replacing oxido donors with sulfido donors), anion exchange of bridging ligands (considering μ-Br<sup>-</sup>, μ-Cl<sup>-</sup>, μ-F<sup>-</sup>, μ-SH<sup>-</sup>, or μ-OH<sup>-</sup> groups), and altering the formal oxidation state of the metal. As a result, we show that it is possible to tune the O<sub>2</sub> affinity at the open metal sites of MOFs for applications involving the strong and/or selective binding of O<sub>2</sub>. In contrast with O<sub>2</sub> adsorption, N<sub>2</sub> adsorption at open metal sites is predicted to be relatively weak across the MOF dataset, with the exception of MOFs containing synthetically elusive V<sup>2+</sup> open metal sites. As one example from the screening study, we predict that exchanging the μ-Cl<sup>-</sup> ligands of M<sub>2</sub>Cl<sub>2</sub>(BBTA) (H<sub>2</sub>BBTA = 1<i>H</i>,5<i>H</i>-benzo(1,2-d:4,5-d′)bistriazole) with μ-OH<sup>-</sup> groups would significantly enhance the strength of O<sub>2</sub> adsorption at the open metal sites without a corresponding increase in the N<sub>2</sub> affinity. Experimental investigation of Co<sub>2</sub>Cl<sub>2</sub>(BBTA) and Co<sub>2</sub>(OH)<sub>2</sub>(BBTA) confirms that the former exhibits only weak physisorption, whereas the latter is capable of chemisorbing O<sub>2</sub> at room temperature. The chemisorption behavior is attributed to the greater electron-donating character of the μ-OH<sup>-</sup><sub> </sub>ligands and the presence of H-bonding interactions between the μ-OH<sup>-</sup> bridging ligands and the O<sub>2</sub> adsorbate.</p>

Exchange-Biasing in a Dinuclear Dysprosium(III) Single-Molecule Magnet with a Large Energy Barrier for Magnetization Reversal

2019 ◽  
Author(s):  
Tian Han ◽  
Marcus J. Giansiracusa ◽  
Zi-Han Li ◽  
You-Song Ding ◽  
Nicholas F. Chilton ◽  
...  
Keyword(s):  
Single Molecule ◽  
Magnetization Reversal ◽  
Energy Barrier ◽  
Magnetic Hysteresis ◽  
Large Energy ◽  
Magnetic Studies ◽  
Bridging Ligands ◽  
Single Molecule Magnet ◽  
Exchange Biasing

A dichlorido-bridged dinuclear dysprosium(III) single-molecule magnet [Dy<sub>2</sub>L<sub>2</sub>(<i>µ</i>-Cl)<sub>2</sub>(THF)<sub>2</sub>] has been made using a diamine-bis(phenolate) ligand, H<sub>2</sub>L. Magnetic studies show an energy barrier for magnetization reversal (<i>U</i><sub>eff</sub>) around 1000 K. Exchange-biasing effect is clearly seen in magnetic hysteresis with steps up to 4 K. <i>Ab</i> initio calculations exclude the possibility of pure dipolar origin of this effect leading to the conclusion that super-exchange <i>via</i> the chloride bridging ligands is important.

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