Twisting and Tilting 1,1 '-Bis(dialkylphosphino)ferrocene Bound to Low Valent Tricarbonylmaganese(I to -I)
The result's identifiers
Result code in 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>
Result on the web
<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>
Alternative languages
Result language
angličtina
Original language name
Twisting and Tilting 1,1 '-Bis(dialkylphosphino)ferrocene Bound to Low Valent Tricarbonylmaganese(I to -I)
Original language description
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).
Czech name
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Czech description
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Classification
Type
J<sub>imp</sub> - Article in a specialist periodical, which is included in the Web of Science database
CEP classification
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OECD FORD branch
10403 - Physical chemistry
Result continuities
Project
—
Continuities
I - Institucionalni podpora na dlouhodoby koncepcni rozvoj vyzkumne organizace
Others
Publication year
2017
Confidentiality
S - Úplné a pravdivé údaje o projektu nepodléhají ochraně podle zvláštních právních předpisů
Data specific for result type
Name of the periodical
Inorganic Chemistry
ISSN
0020-1669
e-ISSN
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Volume of the periodical
56
Issue of the periodical within the volume
23
Country of publishing house
US - UNITED STATES
Number of pages
9
Pages from-to
14688-14696
UT code for WoS article
000417342200033
EID of the result in the Scopus database
2-s2.0-85037626201