@article {43638,
	title = {Electrocatalytic water oxidation by a molecular cobalt complex through a high valent cobalt oxo intermediate},
	journal = {Chemical Communications},
	volume = {52},
	year = {2016},
	month = {AUG},
	pages = {11787-11790},
	abstract = {Biuret-modified tetraamidomacrocyclic cobalt complex [Co-III-bTAML]- is shown to catalyze electrochemical water oxidation at basic pH leading to the formation of O-2. Electrochemical and spectroscopic studies indicate a high valent cobalt oxo intermediate isoelectronic to Co-V(O) as the active oxidant. The kinetic isotope effect of 8.63 indicates an atom proton transfer mechanism.},
	doi = {10.1039/c6cc05773j},
	author = {Das, Debasree and Pattanayak, Santanu and Singh, Kundan K. and Garai, Bikash and Sen Gupta, Sayam}
}
@article {48018,
	title = {Electrocatalytic alcohol oxidation by a molecular iron complex},
	journal = {Faraday Discussions},
	volume = {234},
	year = {2022},
	month = {MAY},
	pages = {42-57},
	type = {Article},
	abstract = {<p>
	An efficient electrochemical method for the selective oxidation of alcohols to their corresponding aldehydes/ketones using a biomimetic iron complex, [(bTAML)Fe-III-OH2](-), as the redox mediator in an undivided electrochemical cell with inexpensive carbon and nickel electrodes using water as an oxygen source is reported. The substrate scope also includes alcohols that contain O and N heteroatoms in the scaffold, which are well tolerated under these reaction conditions. Mechanistic studies show the involvement of a high-valent Fe-V(O) species, [(bTAML)Fe-V(O)](-), formed via PCET (overall 2H(+)/2e(-)) from [(bTAML)Fe-III-OH2](-) at 0.77 V (vs. Fc(+)/Fc). Moreover, electrokinetic studies of the oxidation of C-H bonds indicate a second-order reaction, with the C-H abstraction by Fe-V(O) being the rate-determining step. The overall mechanism, studied using linear free energy relationships and radical clocks, indicates a {\textquoteleft}{\textquoteleft}net hydride{\textquoteright}{\textquoteright} transfer, leading to the oxidation of the alcohol to the corresponding aldehyde or ketone. When the reaction was carried out at pH \&gt; 11, the reaction could be carried out at a similar to 500 mV lower potential than that at pH 8, albeit with reduced reaction rates. The reactive intermediate involved at pH \&gt; 11 is the corresponding one-electron oxidized [(bTAML)Fe-IV(O)](2-) species.</p>
},
	issn = {1359-6640},
	doi = {10.1039/d1fd00074h},
	author = {Kuiry, Himangshu and Das, Debasree and Das, Soumadip and Chakraborty, Soham and Chandra, Bittu and Sen Gupta, Sayam}
}
