Twisting and Tilting 1,1 '-Bis(dialkylphosphino)ferrocene Bound to Low Valent Tricarbonylmaganese(I to -I)

Kód výsledku v IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F61388955%3A_____%2F17%3A00482900" target="_blank" >RIV/61388955:_____/17:00482900 - isvavai.cz</a>

Výsledek na webu

<a href="http://dx.doi.org/10.1021/acs.inorgchem.7b02627" target="_blank" >http://dx.doi.org/10.1021/acs.inorgchem.7b02627</a>

DOI - Digital Object Identifier

<a href="http://dx.doi.org/10.1021/acs.inorgchem.7b02627" target="_blank" >10.1021/acs.inorgchem.7b02627</a>

Jazyk výsledku

angličtina

Název v původním jazyce

Twisting and Tilting 1,1 '-Bis(dialkylphosphino)ferrocene Bound to Low Valent Tricarbonylmaganese(I to -I)

Popis výsledku v původním jazyce

Recently we had reported the noninnocent behavior of 1,1'-bis(diphenylphosphino)ferrocene (dppf) in Fe(CO)(3)dppf [Ringenberg et al., Inorg. Chem., 2017, 56, 7501]. Moving to the left in the periodic table, HMn(CO)(3)(dRpf) where dRpf = dppf (1H) and 1,1'-bis(diisopropylphosphino)ferrocene (dippf) (2H) were synthesized. The hydride ligand was removed by protonation with [(Et2O)(2)H][B(Ar-F)(4)] ([B(Ar-F)(4)](-) = tetrakis [3,5-bis (trifluoromethyl)phenyl]borate), resulting in the rapid evolution of H-2 followed by the formation of an Fe -> Mn interaction. The reaction mechanism was determined by in situ IR experiments which show that directly following protonation both [1](+) and [2](+) offer an open manganese coordination site that allows for the formation of an intramolecular Fe -> Mn dative bond. This process is significantly faster for [2](+) than for [1](+). The reduction chemistry as studied by cyclic voltammetry (CV) reveals that both complexes change from a distorted octahedral coordination with an Fe -> Mn interaction to an open square-pyramidal configuration which is more stable for [1](0) than [2](0). Reoxidation of this square-pyramidal species proceeds more reversibly for 2 versus 1 due to the faster ferrocene ligand reorganization. The electrochemical mechanism was studied by in situ spectroscopic techniques, e.g., IR, UV-vis-NIR (near IR), and EPR spectroelectrochemistry (SEC) as well as by CV simulation. The new complexes described offer an exciting platform for the development of electrocatalysts for the reduction of CO2 to CO, or for proton reduction (2H(+) + 2e(-) -> H-2).

Název v anglickém jazyce

Twisting and Tilting 1,1 '-Bis(dialkylphosphino)ferrocene Bound to Low Valent Tricarbonylmaganese(I to -I)

Popis výsledku anglicky

Recently we had reported the noninnocent behavior of 1,1'-bis(diphenylphosphino)ferrocene (dppf) in Fe(CO)(3)dppf [Ringenberg et al., Inorg. Chem., 2017, 56, 7501]. Moving to the left in the periodic table, HMn(CO)(3)(dRpf) where dRpf = dppf (1H) and 1,1'-bis(diisopropylphosphino)ferrocene (dippf) (2H) were synthesized. The hydride ligand was removed by protonation with [(Et2O)(2)H][B(Ar-F)(4)] ([B(Ar-F)(4)](-) = tetrakis [3,5-bis (trifluoromethyl)phenyl]borate), resulting in the rapid evolution of H-2 followed by the formation of an Fe -> Mn interaction. The reaction mechanism was determined by in situ IR experiments which show that directly following protonation both [1](+) and [2](+) offer an open manganese coordination site that allows for the formation of an intramolecular Fe -> Mn dative bond. This process is significantly faster for [2](+) than for [1](+). The reduction chemistry as studied by cyclic voltammetry (CV) reveals that both complexes change from a distorted octahedral coordination with an Fe -> Mn interaction to an open square-pyramidal configuration which is more stable for [1](0) than [2](0). Reoxidation of this square-pyramidal species proceeds more reversibly for 2 versus 1 due to the faster ferrocene ligand reorganization. The electrochemical mechanism was studied by in situ spectroscopic techniques, e.g., IR, UV-vis-NIR (near IR), and EPR spectroelectrochemistry (SEC) as well as by CV simulation. The new complexes described offer an exciting platform for the development of electrocatalysts for the reduction of CO2 to CO, or for proton reduction (2H(+) + 2e(-) -> H-2).

Druh

J_imp - Článek v periodiku v databázi Web of Science

CEP obor

—

OECD FORD obor

10403 - Physical chemistry

Projekt

—

Návaznosti

I - Institucionalni podpora na dlouhodoby koncepcni rozvoj vyzkumne organizace

Rok uplatnění

2017

Kód důvěrnosti údajů

S - Úplné a pravdivé údaje o projektu nepodléhají ochraně podle zvláštních právních předpisů

Název periodika

Inorganic Chemistry

ISSN

0020-1669

e-ISSN

—

Svazek periodika

56

Číslo periodika v rámci svazku

23

Stát vydavatele periodika

US - Spojené státy americké

Počet stran výsledku

9

Strana od-do

14688-14696

Kód UT WoS článku

000417342200033

EID výsledku v databázi Scopus

2-s2.0-85037626201