Azo NN Bond Cleavage with a Redox-Active Vanadium Compound Involving Metal-Ligand Cooperativity

2012 ◽  
Vol 51 (22) ◽  
pp. 5386-5390 ◽  
Author(s):  
Carsten Milsmann ◽  
Zoë R. Turner ◽  
Scott P. Semproni ◽  
Paul J. Chirik
Keyword(s):  
Bond Cleavage ◽  
Vanadium Compound ◽  
Redox Active ◽  
Metal Ligand

Azo NN Bond Cleavage with a Redox-Active Vanadium Compound Involving Metal-Ligand Cooperativity

2012 ◽  
Vol 124 (22) ◽  
pp. 5482-5486 ◽  
Author(s):  
Carsten Milsmann ◽  
Zoë R. Turner ◽  
Scott P. Semproni ◽  
Paul J. Chirik
Keyword(s):  
Bond Cleavage ◽  
Vanadium Compound ◽  
Redox Active ◽  
Metal Ligand

Co(i) complexes with a tetradentate phenanthroline-based PNNP ligand as a potent new metal–ligand cooperation platform

2020 ◽  
Vol 49 (41) ◽  
pp. 14592-14597
Author(s):  
Nai-Yuan Jheng ◽  
Yusuke Ishizaka ◽  
Yuki Naganawa ◽  
Akira Sekiguchi ◽  
Yumiko Nakajima
Keyword(s):  
Bond Cleavage ◽  
Metal Ligand

A cobalt(i) alkyl complex bearing a tetradentate phenanthroline-based PNNP ligand undergoes dearomatization of the ligand backbone skeleton upon heating and furthermore achieves H–H bond cleavage.

Intramolecular metal–ligand electron transfer triggered by co-ligand substitution

2018 ◽  
Vol 47 (28) ◽  
pp. 9430-9441 ◽  
Author(s):  
Alexandra Ziesak ◽  
Lena Steuer ◽  
Elisabeth Kaifer ◽  
Norbert Wagner ◽  
Johannes Beck ◽  
...  
Keyword(s):  
Electron Transfer ◽  
Ligand Substitution ◽  
Dinuclear Copper ◽  
Redox Active ◽  
Metal Ligand

Labile co-ligands are attached to a dinuclear copper(i) complex with a redox-active bridging guanidine ligand. Their substitution triggers electron-transfer from the copper atoms to the guanidine.

A coordinatively unsaturated iridium complex with an unsymmetrical redox-active ligand: (spectro)electrochemical and reactivity studies

2019 ◽  
Vol 48 (37) ◽  
pp. 13931-13942 ◽  
Author(s):  
Sebastian Sobottka ◽  
Margarethe Behr van der Meer ◽  
Estelle Glais ◽  
Uta Albold ◽  
Simon Suhr ◽  
...  
Keyword(s):  
Bond Activation ◽  
Iridium Complex ◽  
Iridium Complexes ◽  
Redox Active Ligand ◽  
Active Ligand ◽  
Redox Active ◽  
Metal Ligand

Metal–ligand cooperativity can be used in iridium complexes with an unsymmetrically substituted redox-active diamidobenzene ligand for bond activation reactions.

B–H Bond Cleavage via Metal–Ligand Cooperation by Dearomatized Ruthenium Pincer Complexes

2014 ◽  
Vol 33 (14) ◽  
pp. 3716-3726 ◽  
Author(s):  
Aviel Anaby ◽  
Burkhard Butschke ◽  
Yehoshoa Ben-David ◽  
Linda J. W. Shimon ◽  
Gregory Leitus ◽  
...  
Keyword(s):  
Bond Cleavage ◽  
Pincer Complexes ◽  
Metal Ligand

scholarly journals Iron Dissolution from Goethite (α-FeOOH) Surfaces in Water by Ab Initio Enhanced Free Energy Simulations

2018 ◽  
Author(s):  
Konstantin Klyukin ◽  
Kevin Rosso ◽  
Vitaly Alexandrov
Keyword(s):  
Metal Oxides ◽  
Bond Cleavage ◽  
Natural Environments ◽  
Quantum Molecular Dynamics ◽  
Iron Dissolution ◽  
Redox Active ◽  
Complex Process ◽  
Rapid Dissolution ◽  
Energy Simulations ◽  
Dynamics Simulations

<p>Dissolution of redox-active metal oxides plays a key role in a variety of phenomena including (photo)electrocatalysis, degradation of battery materials, corrosion of metal oxides and biogeochemical cycling of metals in natural environments. Despite its widespread significance, mechanisms of metal-oxide dissolution remain poorly understood at the atomistic level. This study is aimed at elucidating the long-standing problem of iron dissolution from Fe(III)-oxide, a complex process involving coupled hydrolysis, surface protonation, electron transfer, and metal-oxygen bond cleavage. We examine the case of goethite (α-FeOOH), a representative phase bearing structural similarities with many other metal (hydr)oxides. By employing quantum molecular dynamics simulations (metadynamics combined with the Blue Moon ensemble approach), we unveil the mechanistic pathways and rates of both nonreductive and reductive dissolution of iron from the (110) and (021) goethite facets in aqueous solutions at room temperature. Our simulations reveal the interplay between concerted internal (structural) and external (from solution) protonation as essential for breaking Fe-O bonds, as well as for stabilizing intermediate configurations of dissolving Fe. We demonstrate specifically how Fe(III) reduction to Fe(II) yields higher dissolution rates than the proton-mediated pathway, while the most rapid dissolution is expected for these two processes combined, in agreement with experiments.</p>

scholarly journals Hydrogenase biomimetics with redox-active ligands: Synthesis, structure and electrocatalytic studies on Fe2(CO)4(K2-dppn)(µ-edt) (edt = ethanedithiolate; dppn = 1,8-bis(diphenylphosphino)naphthalene)

2018 ◽  
Author(s):  
Graeme Hogarth ◽  
Shishir Ghosh ◽  
Nathan Hollingsworth ◽  
Michael Richmond ◽  
Shariff Kabir ◽  
...  
Keyword(s):  
Bond Cleavage ◽  
Major Product ◽  
Proton Reduction ◽  
Catalytic Current ◽  
Redox Active Ligands ◽  
Hydride Complexes ◽  
Redox Active ◽  
Active Nature ◽  
Strong Acids ◽  
Reversible Reduction

Addition of the bulky redox-active diphosphine 1,8-bis(diphenylphosphino)naphthalene (dppn) to [Fe2(CO)6(-edt)] (1) (edt = 1,2-ethanedithiolate) affords [Fe2(CO)4(2-dppn)(-edt)] (3) as the major product, together with small amounts of a P-C bond cleavage product [Fe2(CO)5{1-PPh2(1-C10H7)}(-edt)] (2). The redox properties of 3 have been examined by cyclic voltammetry and it has been tested as a proton-reduction catalyst. It undergoes a reversible reduction at E1/2 = &ndash;2.18 V and exhibits two overlapping reversible oxidations at E1/2 = &ndash;0.08 V and E1/2 = 0.04 V. DFT calculations show that while the HOMO is metal-centred (Fe-Fe -bonding), the LUMO is primarily ligand-based but also contains an antibonding Fe-Fe contribution, highlighting the redox-active nature of the diphosphine. It is readily protonated upon addition of strong acids to afford two isomeric hydride complexes and catalyzes the electrochemical reduction of protons at Ep = &ndash;2.00 V in the presence of CF3CO2H. The catalytic current indicates that it is one of the most efficient diiron electrocatalysts for the reduction of protons, albeit operating at quite negative potential.

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