Redox Potentials of High‐Valent Iron‐, Cobalt‐, and Nickel‐Oxido Complexes: Evidence for Exchange Enhanced Reactivity

The ferrocene titration method has been employed to determine the one‐electron reduction potentials of a series of oxido‐iron(IV), oxido‐cobalt(IV) and oxido/hydroxido‐nickel(III) complexes based on the same tetradentate TMG3tren ligand (TMG3tren=tris[2‐(N‐tetramethylguanidyl)ethyl]amine). The S=2 ground state of the [(TMG3tren)FeIV=O]2+ complex allows an exchange enhanced reactivity, which enables it to perform efficient oxygen atom transfer (OAT) and hydrogen atom abstraction (HAA) reactions with a low one‐electron reduction potential of 270 mV vs. SCE. In the absence of exchange enhanced reactivity, the OAT and HAA abilities of the S=3/2 [(TMG3tren)CoIV−O(Sc(OTf)3)]2+, S=1/2 [(TMG3tren)NiIII−O(H)]2+ and the previously reported S=1 [(TMC)(CH3CN)FeIV=O]2+ and [(N4Py)FeIV=O]2+ complexes can be directly correlated to their reduction potentials. Notably, [(N4Py)FeIV=O]2+ and [(TMG3tren)FeIV=O]2+ exhibit similar OAT and HAA reactivities although the reduction potential of [(N4Py)FeIV=O]2+ is 0.24 V more positive than that of [(TMG3tren)FeIV=O]2+. The present study therefore provides experimental evidence for exchange enhanced reactivity and rationalizes nature's choice for employing S=2 oxido‐iron(IV) cores to achieve difficult oxidation reactions at biologically viable potentials.Heidelberg UniversityDeutsche Forschungsgemeinschaft http://dx.doi.org/10.13039/501100001659Peer Reviewe

Modelling the coordination environment in α-ketoglutarate dependent oxygenases – a comparative study on the effect of N- vs. O-ligation

In various non-heme iron oxygenases the Fe(II) center is coordinated by 2 N and 1 O atoms of the 2-His-2-carboxylate facial triad; however, most artificial model complexes bear only N-based ligands. In an effort to closely mimic the coordination environment in α-ketoglutarate dependent oxygenases, we have now employed the Me2tacnO ligand (4,7-dimethyl-1-oxa-4,7-diazacyclononane) in the synthesis of the complexes [(Me2tacnO)FeCl2]2 (1-NNO), [(Me2tacnO)FeCl3] (1 b-NNO) and [(Me2tacnO)Fe(BF)Cl] (2-NNO; BF=benzoylformate). The weaker donation of the O atom in the ligand was found to result in stronger binding of the ligand in trans-position to the O-atom of the ancillary ligand as compared to the corresponding complexes involving the Me3tacn (1,4,7-trimethyl-1,4,7-triazacyclononane) ligand. Furthermore, by stopped-flow techniques we could detect an intermediate (3-NNO) in the reaction of 2-NNO with O2. The spectroscopic features of 3-NNO agree with the involvement of an Fe(IV)-oxo intermediate and hence this study represents the first detection of such an intermediate in the O2 activation of artificial α-ketoglutarate Fe(II) complexes

Modelling the coordination environment in α‐ketoglutarate dependent oxygenases – a comparative study on the effect of N‐ vs. O‐ligation

In various non-heme iron oxygenases the Fe(II) center is coordinated by 2 N and 1 O atoms of the 2-His-2-carboxylate facial triad; however, most artificial model complexes bear only N-based ligands. In an effort to closely mimic the coordination environment in α-ketoglutarate dependent oxygenases, we have now employed the Me2tacnO ligand (4,7-dimethyl-1-oxa-4,7-diazacyclononane) in the synthesis of the complexes [(Me2tacnO)FeCl2]2 (1-NNO), [(Me2tacnO)FeCl3] (1 b-NNO) and [(Me2tacnO)Fe(BF)Cl] (2-NNO; BF=benzoylformate). The weaker donation of the O atom in the ligand was found to result in stronger binding of the ligand in trans-position to the O-atom of the ancillary ligand as compared to the corresponding complexes involving the Me3tacn (1,4,7-trimethyl-1,4,7-triazacyclononane) ligand. Furthermore, by stopped-flow techniques we could detect an intermediate (3-NNO) in the reaction of 2-NNO with O2. The spectroscopic features of 3-NNO agree with the involvement of an Fe(IV)-oxo intermediate and hence this study represents the first detection of such an intermediate in the O2 activation of artificial α-ketoglutarate Fe(II) complexes.Deutsche Forschungsgemeinschaft (DFG, German Research Foundation)Peer Reviewe

Spektroskopische Charakterisierung eines reaktiven [Cu2(μ‐OH)2]2+ Intermediates in Cu/TEMPO‐katalysierten aeroben Alkoholoxidationen

CuI/TEMPO-Katalysatorsysteme (TEMPO=2,2,6,6-Tetramethylpiperidinoxyl) sind vielseitige Katalysatoren für aerobe Alkoholoxidationsreaktionen zur selektiven Synthese von Aldehyden. Jedoch sind mehrere Aspekte des Reaktionsmechanismus noch nicht aufgeklärt, was hauptsächlich daran liegt, dass bisher keine reaktiven Intermediate identifiziert werden konnten. Wir zeigen hier die Synthese und Charakterisierung eines dinuklearen Komplexes [L12Cu2]2+ (1), der in Gegenwart von TEMPO die katalytische 4 H+/4 e− Reduktion von O2 zu Wasser an die Oxidation von benzylischen und aliphatischen Alkoholen koppeln kann. Die Mechanismen der katalytischen O2-Reduktion und der Alkoholoxidation wurden sowohl durch spektroskopische Detektion der reaktiven Intermediate in der Gas- und der kondensierten Phase als auch durch kinetische Studien an jedem Reaktionsschritt in den Katalysezyklen aufgeklärt. Die intermediären Bis(μ-oxido)dikupfer(III)- (2) und Bis(μ-hydroxido)dikupfer(II)-Spezies (3) wurden als wichtige Reaktanden in beiden Reaktionen identifiziert. Die vorliegende Studie ermöglicht tiefgehende mechanistische Einblicke in die aerobe Alkoholoxidation, die eine wertvolle Grundlage bieten um übergangsmetallkatalysierte Reaktionen mit redoxaktiven Cokatalysatoren besser zu verstehen.Peer Reviewe

Effect of integrated nutrient management on the nutrient accumulation and status of post-harvest soil of brinjal (Solanum melongena L.) under Nadia conditions (West Bengal), India

A field experiment was carried out at the Central Research Farm, Bidhan Chandra Krishi Viswavidyalaya, West Bengal, India to study the effects of integrated nutrient management on the nutrient accumulation (dry weight recoveries) in brinjal and plant nutrient status of the post- harvest soil of brinjal under Nadia conditions. The results revealed that the treatment consisting of 75% RDF (RDF i.e. N:P:K:: 125:100:50) + Azospirillum + phosphate solubilising bacteria (PSB) + Borax @ 10 kg ha-1 recorded the highest oxidizable organic carbon (8.049 g kg-1), total nitrogen (1.05 g kg-1) , available nitrogen (212.67g kg-1), available phosphorus (76.20g kg-1) and available potassium (177.59 g kg-1) in the post harvest soils of brinjal. On the other hand, 75% RDF + Azospirillum + PSB + FeSO4 @ 50 kg ha-1 recorded the highest available iron (26.14 kg ha-1) and the treatment consisting of 75% RDF + Azospirillum + PSB + ZnSOâ‚„ @ 25 kg ha-1 recorded the highest soil available zinc (7.62 kg ha-1) while 75% RDF + Azo + PSB + Borax @ 10 kg ha-1 recorded the highest available Boron content (0.78 kg ha-1) of the post harvest soil of Brinjal. Highest brinjal yield (14.96 t ha-1) was supported by the treatment consisting of 75% RDF + Azospirillum + PSB + Boron @ 10 Kg ha-1. Meager information was available regarding the performance of integrated application of organics and micronutrient on brinjal in the experimental location. The present study may enlighten this unexplored section of nutrient management in brinjal

Stable, but still reactive – investigations on the effects of Lewis acid binding on copper nitrene intermediates

Copper nitrenes are proposed as reactive intermediates in a number of copper mediated aziridination and amination reactions. However, the isolation and characterization of such intermediates have proved challenging because of their transient nature. One successful approach for the stabilization of the copper-nitrene cores is the employment of a redox innocent Lewis acid (LA) like Sc3+. We herein report the stabilization of two transient copper nitrene species 3 and 4 in the absence of LAs by employing electronegative −CF3 and −NO2 groups in the nitrene substituent. Detailed investigations of the spectroscopic properties of 3 and 4 by theoretical and experimental methods, and a comparison of their reactivities in presence and absence of LAs provide some vital insights into the effect of LAs on the geometric and electronic structures of the copper nitrenes