Metalloradical Compounds with 1,2-Dipivaloylhydrazido Ligands: Electron Transfer and Alkylation/Protonation Effects
Identifikátory výsledku
Kód výsledku v IS VaVaI
<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F61388955%3A_____%2F19%3A00505695" target="_blank" >RIV/61388955:_____/19:00505695 - isvavai.cz</a>
Výsledek na webu
<a href="http://hdl.handle.net/11104/0297107" target="_blank" >http://hdl.handle.net/11104/0297107</a>
DOI - Digital Object Identifier
<a href="http://dx.doi.org/10.1002/ejic.201900391" target="_blank" >10.1002/ejic.201900391</a>
Alternativní jazyky
Jazyk výsledku
angličtina
Název v původním jazyce
Metalloradical Compounds with 1,2-Dipivaloylhydrazido Ligands: Electron Transfer and Alkylation/Protonation Effects
Popis výsledku v původním jazyce
Under oxidative conditions the complexes M(bpy)2Cl2, M = Ru or Os, react with 1,2-dipivaloylhydrazine H2L = tBuC(O)-NH-NH-C(O)-tBu to yield the paramagnetic compounds [M(L)(bpy)2](PF6) {1(PF6), M = Ru and 2(PF6), M = Os}. Crystal structures of 1(ClO4) and 2(PF6) reveal an NNCO chelate coordination of L with d(NN) ≈ 1.39 Å. EPR spectroscopy suggests a metal/ligand mixed situation for the unpaired electron, with 29 % (Ru, 1+) or 46 % (Os, 2+) metal spin contribution according to DFT calculations. Both complex cations exhibit reversible one-electron oxidation and reduction (Kc ≈ 1019 for 1+ and 1012 for 2+) which could also be monitored by IR (νCO) and UV/Vis-NIR spectroelectrochemistry. These data confirm a metal/ligand orbital mixing MII(L·–) ↔ MIII(L2–), with the osmium analogue favoring the latter alternative. Reaction of Ru(bpy)2Cl2 under non-oxidizing conditions yields the intermediate (1H)(PF6) which could be oxidatively deprotonated to 1+ or methylated to (1Me)(PF6), both identified by 1H and 13C NMR. While oxidation of (1H)+ proceeds irreversibly due to proton loss, the reversible spectroelectrochemical oxidation of (1Me)+ suggests a metal-based process RuII(LMe–) → RuIII(LMe–). The results reveal that not only dinuclear complexes of 1,2-diacylhydrazido ligands but also mononuclear analogues are distinguished by remarkably variable metal/ligand mixed contributions to the frontier orbitals.
Název v anglickém jazyce
Metalloradical Compounds with 1,2-Dipivaloylhydrazido Ligands: Electron Transfer and Alkylation/Protonation Effects
Popis výsledku anglicky
Under oxidative conditions the complexes M(bpy)2Cl2, M = Ru or Os, react with 1,2-dipivaloylhydrazine H2L = tBuC(O)-NH-NH-C(O)-tBu to yield the paramagnetic compounds [M(L)(bpy)2](PF6) {1(PF6), M = Ru and 2(PF6), M = Os}. Crystal structures of 1(ClO4) and 2(PF6) reveal an NNCO chelate coordination of L with d(NN) ≈ 1.39 Å. EPR spectroscopy suggests a metal/ligand mixed situation for the unpaired electron, with 29 % (Ru, 1+) or 46 % (Os, 2+) metal spin contribution according to DFT calculations. Both complex cations exhibit reversible one-electron oxidation and reduction (Kc ≈ 1019 for 1+ and 1012 for 2+) which could also be monitored by IR (νCO) and UV/Vis-NIR spectroelectrochemistry. These data confirm a metal/ligand orbital mixing MII(L·–) ↔ MIII(L2–), with the osmium analogue favoring the latter alternative. Reaction of Ru(bpy)2Cl2 under non-oxidizing conditions yields the intermediate (1H)(PF6) which could be oxidatively deprotonated to 1+ or methylated to (1Me)(PF6), both identified by 1H and 13C NMR. While oxidation of (1H)+ proceeds irreversibly due to proton loss, the reversible spectroelectrochemical oxidation of (1Me)+ suggests a metal-based process RuII(LMe–) → RuIII(LMe–). The results reveal that not only dinuclear complexes of 1,2-diacylhydrazido ligands but also mononuclear analogues are distinguished by remarkably variable metal/ligand mixed contributions to the frontier orbitals.
Klasifikace
Druh
J<sub>imp</sub> - Článek v periodiku v databázi Web of Science
CEP obor
—
OECD FORD obor
10403 - Physical chemistry
Návaznosti výsledku
Projekt
<a href="/cs/project/GA18-09848S" target="_blank" >GA18-09848S: Fotoelektrochemická redukce oxidu uhličitého na měděných pěnových elektrodách modifikovaných oxidy mědi</a><br>
Návaznosti
I - Institucionalni podpora na dlouhodoby koncepcni rozvoj vyzkumne organizace
Ostatní
Rok uplatnění
2019
Kód důvěrnosti údajů
S - Úplné a pravdivé údaje o projektu nepodléhají ochraně podle zvláštních právních předpisů
Údaje specifické pro druh výsledku
Název periodika
European Journal of Inorganic Chemistry
ISSN
1434-1948
e-ISSN
—
Svazek periodika
2019
Číslo periodika v rámci svazku
21
Stát vydavatele periodika
DE - Spolková republika Německo
Počet stran výsledku
9
Strana od-do
2639-2647
Kód UT WoS článku
000471072200012
EID výsledku v databázi Scopus
2-s2.0-85065655755