Diiron Carbonyl Complexes Bearing an N,C,S-Pincer Ligand: Reactivity toward Phosphines, Heterolytic Fe–Fe Cleavage, and Electrocatalytic Proton Reduction

2014 ◽  
Vol 33 (16) ◽  
pp. 4260-4268 ◽  
Author(s):  
Masakazu Hirotsu ◽  
Kiyokazu Santo ◽  
Chiaki Tsuboi ◽  
Isamu Kinoshita
Keyword(s):  
Carbonyl Complexes ◽  
Pincer Ligand ◽  
Proton Reduction ◽  
Ligand Reactivity

Electrocatalytic proton reduction by dithiolate-bridged diiron carbonyl complexes: a connection to the H-cluster?

2005 ◽  
Vol 33 (1) ◽  
pp. 3-6 ◽  
Author(s):  
S.J. Borg ◽  
M.I. Bondin ◽  
S.P. Best ◽  
M. Razavet ◽  
X. Liu ◽  
...  
Keyword(s):  
New Species ◽  
Reaction Scheme ◽  
Carbonyl Groups ◽  
Carbonyl Complexes ◽  
Electrochemical Investigation ◽  
Proton Reduction ◽  
Rate Limiting ◽  
A New Species ◽  
Sequential Electron ◽  
Electrocatalytic Reaction

Spectroscopic and electrochemical investigation of electrocatalytic proton reduction by Fe2(μ-pdt)(CO)6, 1, have been interpreted in terms of a reaction scheme involving sequential electron–proton reactions to give a two-electron, two-proton product that undergoes rate-limiting dihydrogen elimination. Further reduction, at slightly higher negative potentials, gives a more reactive product and this process dominates reactions conducted at higher acid concentrations. Inhibition of the electrocatalytic reaction by CO is due to the more efficient loss of catalyst and this is best modelled by a reaction that is second order in terms of 1−. During electrocatalytic proton reduction a new species is observed, which features a bridging CO group and the wavenumbers of the ν(CO) modes of the terminally bound carbonyl groups are similar to those of the carbonyl groups bound to the oxidized form of the H-cluster.

Coordination Chemistry of the PdmBOX Pincer Ligand: Reactivity at the Metal and the Ligand

2017 ◽  
Vol 2017 (47) ◽  
pp. 5545-5556 ◽  
Author(s):  
Jan Wenz ◽  
Vladislav Vasilenko ◽  
Alexander Kochan ◽  
Hubert Wadepohl ◽  
Lutz H. Gade
Keyword(s):  
Coordination Chemistry ◽  
Pincer Ligand ◽  
Ligand Reactivity

Synthesis and characterization of new M(II) carbonyl complexes (M = Fe or Ru) including an η1-N-maleimidato ligand. Reactivity studies with biological thiols

2016 ◽  
Vol 801 ◽  
pp. 101-110 ◽  
Author(s):  
Bogna Rudolf ◽  
Aleksandra Kubicka ◽  
Michèle Salmain ◽  
Marcin Palusiak ◽  
Agnieszka J. Rybarczyk-Pirek ◽  
...  
Keyword(s):  
Synthesis And Characterization ◽  
Carbonyl Complexes ◽  
Ligand Reactivity

Amido Complexes of Iridium with a PNP Pincer Ligand: Reactivity toward Alkynes and Hydroamination Catalysis

2018 ◽  
Vol 37 (15) ◽  
pp. 2618-2629 ◽  
Author(s):  
Pablo Hermosilla ◽  
Pablo López ◽  
Pilar García-Orduña ◽  
Fernando J. Lahoz ◽  
Víctor Polo ◽  
...  
Keyword(s):  
Pincer Ligand ◽  
Amido Complexes ◽  
Ligand Reactivity

Electrochemical proton reduction catalysed by selenolato-manganese carbonyl complexes

RSC Advances ◽  
2015 ◽  
Vol 5 (49) ◽  
pp. 39303-39309 ◽  
Author(s):  
Kaipeng Hou ◽  
Sherman J. L. Lauw ◽  
Richard D. Webster ◽  
Wai Yip Fan
Keyword(s):  
Carbonyl Complexes ◽  
Proton Reduction ◽  
Manganese Carbonyl

Four manganese selenolato carbonyl complexes have been synthesized and used as electrocatalyst for proton reduction.

MULTIPLE SCATTERING EFFECTS IN THE COBALT K-EDGE EXAFS OF METAL CARBONYL COMPLEXES

1986 ◽  
Vol 47 (C8) ◽  
pp. C8-589-C8-592
Author(s):  
N. BINSTED ◽  
S. L. COOK ◽  
J. EVANS ◽  
R. J. PRICE ◽  
G. N. GREAVES
Keyword(s):  
Multiple Scattering ◽  
Metal Carbonyl ◽  
Carbonyl Complexes ◽  
Metal Carbonyl Complexes ◽  
Scattering Effects ◽  
Multiple Scattering Effects

An NADH-Inspired Redox Mediator Strategy to Promote Second-Sphere Electron and Proton Transfer for Cooperative Electrochemical CO2 Reduction Catalyzed by Iron Porphyrin

2020 ◽  
Author(s):  
Peter T. Smith ◽  
Sophia Weng ◽  
Christopher Chang
Keyword(s):  
Proton Transfer ◽  
Co2 Reduction ◽  
Iron Porphyrin ◽  
Redox Mediators ◽  
Reservoir Properties ◽  
Proton Reduction ◽  
Electrochemical Co2 Reduction ◽  
Starting Point ◽  
Rate Improvement ◽  
Molecular Catalysts

We present a bioinspired strategy for enhancing electrochemical carbon dioxide reduction catalysis by cooperative use of base-metal molecular catalysts with intermolecular second-sphere redox mediators that facilitate both electron and proton transfer. Functional synthetic mimics of the biological redox cofactor NADH, which are electrochemically stable and are capable of mediating both electron and proton transfer, can enhance the activity of an iron porphyrin catalyst for electrochemical reduction of CO<sub>2</sub> to CO, achieving a 13-fold rate improvement without altering the intrinsic high selectivity of this catalyst platform for CO<sub>2</sub> versus proton reduction. Evaluation of a systematic series of NADH analogs and redox-inactive control additives with varying proton and electron reservoir properties reveals that both electron and proton transfer contribute to the observed catalytic enhancements. This work establishes that second-sphere dual control of electron and proton inventories is a viable design strategy for developing more effective electrocatalysts for CO<sub>2</sub> reduction, providing a starting point for broader applications of this approach to other multi-electron, multi-proton transformations.

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