Why intermolecular nitric oxide (NO) transfer? Exploring the factors and mechanistic aspects of NO transfer reaction

Abstract

Small molecule activation & their transfer reactions in biological or catalytic reactions are greatly influenced by the metal-centers and the ligand frameworks. Here, we report the metal-directed nitric oxide (NO)...

Acid-induced nitrite reduction of nonheme iron(ii)-nitrite: mimicking biological Fe–NiR reactions

“…40 b ,52 The mechanistic aspects of NiR chemistry mediated by H + are still challenging to the scientific community and yet to be resolved as two different side products have been proposed to form in vivo and in vitro studies. 8 a ,9,16,25,30 Also, the pH/or H + ion concentration effect is yet to be confirmed as it affects the reaction mechanism and the side products of NO 2 − reduction reactions. 48 In this report, we have shown the reduction of NO 2 − in a nonheme Fe II -nitrito complex, [(12TMC)Fe II (NO 2 − )] + ( 2 ), to an Fe–nitrosyl complex [(12TMC)Fe(NO)] 2+ , {FeNO} 7 ( 3 ), in the presence of different equivalents of H + (CF 3 SO 3 D, D + ion source), a biomimetic functional model of NiR.…”

“…In addition to the developments on biomimetic synthetic modeling of M–NOs/or active sites associated with NiR and/or NOS. 11 d ,30 Recently, Lehnert and coworkers have established the synthetic strategy for Fe–NOs, 31 and Nam and coworkers have explored the photo-induced NiR reactivity of Fe–NO 2 − to generate Fe–NOs and also stabilize Co–NOs. 32 Ford and coworkers continuously discover the NiR chemistry of various heme systems.…”

Mechanistic insights into nitric oxide oxygenation (NOO) reactions of {CrNO}5 and {CoNO}8

“…S17†). 52 Cyclic voltammetric measurements of 4 showed a quasi-reversible cyclic voltammogram, clearly different from that of 2 , suggesting a completely new species (ESI, Fig. S16b and c†).…”

“…Complex 2 was synthesized and isolated by following our previous report. 43 The addition of one equivalent of O 2 ˙ − (KO 2 /18-crown-6) to a CH 3 CN solution of 2 under Ar showed a color change from light green to dark red at 298 K. Upon reaction of 2 with O 2 ˙ − , the characteristic UV-vis absorption bands of 2 (black line, λ max = 600 nm) changed to a new band (blue line, λ max = 450 nm) within ∼one minute (Fig. 5a), which gradually changed to the red line (NO-oxidized product, 4 ) in ∼five minutes (Fig.…”

“…24,33e,35b,42 Thus, to understand the NO oxidation reactions of metal-nitrosyl complexes, we prepared {CrNO} 5 (S = 1/2) and {CoNO} 8 (S = 0), having different spin states/magnetic properties with similar ligand frameworks. Therefore, [(BPMEN)Co(NO)] 2+ ({CoNO} 8 , 1) and [(BPMEN)Cr(NO)(Cl − )] + ({CrNO} 5 , 2) complexes 43 (BPMEN = N,N′-bis(2-pyridylmethyl)-1,2-diaminoethane) were explored for their reactivity towards O 2…”