scholarly journals Redox-Active Bis(phenolate) N-Heterocyclic Carbene [OCO] Pincer Ligands Support Cobalt Electron Transfer Series Spanning Four Oxidation States

2017 ◽  
Vol 56 (20) ◽  
pp. 12421-12435 ◽  
Author(s):  
Caleb F. Harris ◽  
Michael B. Bayless ◽  
Nicolaas P. van Leest ◽  
Quinton J. Bruch ◽  
Brooke N. Livesay ◽  
...  
2021 ◽  
Author(s):  
Kate Jesse ◽  
Mu-Chieh Chang ◽  
Alexander S. Filatov ◽  
John Anderson

<div>Nature uses control of the secondary coordination sphere</div><div>to facilitate an astounding variety of transformations. Similarly, synthetic chemists have found metal-ligand cooperativity to be a powerful strategy for designing complexes that can mediate challenging reactivity. In particular, this strategy has been used to facilitate two electron reactions with first row transition metals that</div><div>more typically engage in one electron redox processes. While NNN pincer ligands feature prominently in this area, examples which can potentially engage in both proton and electron transfer are less common. Dihydrazonopyrrole (DHP) ligands have been isolated in a variety of redox and protonation states when complexed to Ni. However, the redox-state of this ligand scaffold is less obvious when</div><div>complexed to metal centers with more accessible redox couples. Here, we synthesize a new series of Fe-DHP complexes in two distinct oxidation states. Detailed characterization supports that the redox chemistry</div><div>in this set is still primarily ligand based. Finally, these</div><div>complexes exist as 5-coordinate species with an open coordination site offering the possibility of enhanced reactivity.</div>


2021 ◽  
Author(s):  
Kate Jesse ◽  
Mu-Chieh Chang ◽  
Alexander S. Filatov ◽  
John Anderson

<div>Nature uses control of the secondary coordination sphere</div><div>to facilitate an astounding variety of transformations. Similarly, synthetic chemists have found metal-ligand cooperativity to be a powerful strategy for designing complexes that can mediate challenging reactivity. In particular, this strategy has been used to facilitate two electron reactions with first row transition metals that</div><div>more typically engage in one electron redox processes. While NNN pincer ligands feature prominently in this area, examples which can potentially engage in both proton and electron transfer are less common. Dihydrazonopyrrole (DHP) ligands have been isolated in a variety of redox and protonation states when complexed to Ni. However, the redox-state of this ligand scaffold is less obvious when</div><div>complexed to metal centers with more accessible redox couples. Here, we synthesize a new series of Fe-DHP complexes in two distinct oxidation states. Detailed characterization supports that the redox chemistry</div><div>in this set is still primarily ligand based. Finally, these</div><div>complexes exist as 5-coordinate species with an open coordination site offering the possibility of enhanced reactivity.</div>


Author(s):  
Jingtao Duan ◽  
Zhiyuan Xu ◽  
Zhen Yang ◽  
Jie Jiang

Redox-active humic acids (HA) are ubiquitous in terrestrial and aquatic systems and are involved in numerous electron transfer reactions affecting biogeochemical processes and fates of pollutants in soil environments. Redox-active contaminants are trapped in soil micropores (<2 nm) that have limited access to microbes and HA. Therefore, the contaminants whose molecular structure and properties are not damaged accumulate in the soil micropores and become potential pollution sources. Electron transfer capacities (ETC) of HA reflecting redox activities of low molecular weight fraction (LMWF, <2.5) HA can be detected by an electrochemical method, which is related to redox potentials (Eh) in soil and aquatic environments. Nevertheless, electron accepting capacities (EAC) and electron donating capacities (EDC) of these LMWF HA at different Eh are still unknown. EDC and EAC of different molecular weight HA at different Eh were analyzed using electrochemical methods. EAC of LMWF at −0.59 V was 12 times higher than that at −0.49 V, while EAC increased to 2.6 times when the Eh decreased from −0.59 V to −0.69 V. Afterward, LMWF can act as a shuttle to stimulate microbial Fe(III) reduction processes in microbial reduction experiments. Additionally, EAC by electrochemical analysis at a range of −0.49–−0.59 V was comparable to total calculated ETC of different molecular weight fractions of HA by microbial reduction. Therefore, it is indicated that redox-active functional groups that can be reduced at Eh range of −0.49–−0.59 are available to microbial reduction. This finding contributes to a novel perspective in the protection and remediation of the groundwater environment in the biogeochemistry process.


2021 ◽  
Author(s):  
Dai Oyama ◽  
Takatoshi Kanno ◽  
Tsugiko Takase

Quinone derivatives and their metal complexes are well-known molecules that participate in electron-transfer reactions relevant to diverse fields. However, the fundamental knowledge on the unique reactivity of redox-active quinone complexes...


Geoderma ◽  
2022 ◽  
Vol 408 ◽  
pp. 115580
Author(s):  
Duyen Minh Pham ◽  
Hiroshi Oji ◽  
Shinya Yagi ◽  
Satoshi Ogawa ◽  
Arata Katayama

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