Mechanistic studies on hydrazido(2–)-complexes. Cleavage of the nitrogen–nitrogen bond in the reaction of [Mo{NN(CH2)4CH2}(Ph2PCH2CH2PPh2)2] with acid

Author(s):  
Richard A. Henderson ◽  
G. Jeffery Leigh ◽  
Christopher J. Pickett
2020 ◽  
Author(s):  
Hiroki Toda ◽  
Kazunari Nakajima ◽  
Ken Sakata ◽  
Yoshiaki Nishibayashi

Base metal-catalyzed oxidative conversion of ammonia into dinitrogen is a promising process to utilize ammonia as an energy carrier. In this study, we report the manganese-catalyzed ammonia oxidation under chemical and electrochemical conditions. Mechanistic studies including density functional theory (DFT) calculations suggest that a nucleophilic attack of ammonia on manganese nitrogenous complexes occurs to form a nitrogen–nitrogen bond leading to dinitrogen.<br>


Author(s):  
Hiroki Toda ◽  
Kazunari Nakajima ◽  
Ken Sakata ◽  
Yoshiaki Nishibayashi

Base metal-catalyzed oxidative conversion of ammonia into dinitrogen is a promising process to utilize ammonia as an energy carrier. In this study, we report the manganese-catalyzed ammonia oxidation under chemical and electrochemical conditions. Mechanistic studies including density functional theory (DFT) calculations suggest that a nucleophilic attack of ammonia on manganese nitrogenous complexes occurs to form a nitrogen–nitrogen bond leading to dinitrogen.<br>


2015 ◽  
Vol 44 (1) ◽  
pp. 54-57 ◽  
Author(s):  
Takahiko Ogawa ◽  
Tatsuya Suzuki ◽  
Nicholas M. Hein ◽  
Fraser S. Pick ◽  
Michael D. Fryzuk

The unexpected reaction of a Fe(ii) enamidophosphazide complex with KBEt3H, which results in the elimination of N2 and 1,3-Me2C6H4 to generate a dinuclear Fe(ii) derivative with bridging phosphinimido units, is presented along with mechanistic studies.


2016 ◽  
Vol 228 (06/07) ◽  
Author(s):  
WP Roos ◽  
M Eich ◽  
S Quiros ◽  
AV Knizhnik ◽  
T Nikolova ◽  
...  

Author(s):  
Jack Rowbotham ◽  
Oliver Lenz ◽  
Holly Reeve ◽  
Kylie Vincent

<p></p><p>Chemicals labelled with the heavy hydrogen isotope deuterium (<sup>2</sup>H) have long been used in chemical and biochemical mechanistic studies, spectroscopy, and as analytical tracers. More recently, demonstration of selectively deuterated drug candidates that exhibit advantageous pharmacological traits has spurred innovations in metal-catalysed <sup>2</sup>H insertion at targeted sites, but asymmetric deuteration remains a key challenge. Here we demonstrate an easy-to-implement biocatalytic deuteration strategy, achieving high chemo-, enantio- and isotopic selectivity, requiring only <sup>2</sup>H<sub>2</sub>O (D<sub>2</sub>O) and unlabelled dihydrogen under ambient conditions. The vast library of enzymes established for NADH-dependent C=O, C=C, and C=N bond reductions have yet to appear in the toolbox of commonly employed <sup>2</sup>H-labelling techniques due to requirements for suitable deuterated reducing equivalents. By facilitating transfer of deuterium atoms from <sup>2</sup>H<sub>2</sub>O solvent to NAD<sup>+</sup>, with H<sub>2</sub> gas as a clean reductant, we open up biocatalysis for asymmetric reductive deuteration as part of a synthetic pathway or in late stage functionalisation. We demonstrate enantioselective deuteration via ketone and alkene reductions and reductive amination, as well as exquisite chemo-control for deuteration of compounds with multiple unsaturated sites.</p><p></p>


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