Synthesis, structure, photochemical and electrochemical properties of α-germyl ferrocenyl ketones
The result's identifiers
Result code in IS VaVaI
<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F00216208%3A11310%2F25%3A10506837" target="_blank" >RIV/00216208:11310/25:10506837 - isvavai.cz</a>
Result on the web
<a href="https://verso.is.cuni.cz/pub/verso.fpl?fname=obd_publikace_handle&handle=nHuOJ8WfxE" target="_blank" >https://verso.is.cuni.cz/pub/verso.fpl?fname=obd_publikace_handle&handle=nHuOJ8WfxE</a>
DOI - Digital Object Identifier
<a href="http://dx.doi.org/10.1039/d5dt02029h" target="_blank" >10.1039/d5dt02029h</a>
Alternative languages
Result language
angličtina
Original language name
Synthesis, structure, photochemical and electrochemical properties of α-germyl ferrocenyl ketones
Original language description
Owing to their well-defined and tunable properties, acylgermanes are attractive photoinitiators for polymerization reactions. This paper focuses on the previously unexplored acylgermanes containing the ferrocenylcarbonyl group. For example, compound FcC(O)Ge(SiMe3)3 (4, Fc = ferrocenyl) was synthesized from the reaction of (chlorocarbonyl)ferrocene with the germanide K[Ge(SiMe3)3] generated from KOtBu and tetrakis(trimethylsilyl)germane (1) in a continuous flow setup. In contrast, a complete replacement of the silyl groups in 1 in the presence of KOtBu and KF under conventional conditions produced the tetraacylgermane (FcC(O))4Ge (5). Additionally, mixed-acyl compounds, (FcC(O))(n)Ge(C(O)Mes)(4-n) (n = 1: 6, n = 2: 7; Mes = mesityl), were obtained by salt metathesis of the respective germenolates K(n)Ge(C(O)Mes)(4-n) (2 and 3) with FcC(O)Cl. All compounds, along with the model silane FcC(O)Si(SiMe3)3 (4Si), prepared from in situ-generated KSi(SiMe3)3 and FcC(O)Cl, were fully characterized by elemental analysis, NMR and UV-vis spectroscopy, single-crystal X-ray diffraction analysis, and their electrochemical properties were studied using voltammetric techniques. Compounds bearing exclusively ferrocenoyl substituents were photoinert, whereas mixed ferrocenoyl/mesitoyl derivatives showed alpha-cleavage upon visible-light irradiation. Remarkably, this reactivity extended up to 550 nm, representing the longest wavelength reported for alpha-cleavage in acylgermanes and underscoring their potential for mild, visible-light-driven applications. Preliminary experiments suggested a limited reactivity of 4 and 4Si, likely due to steric effects. Only the reaction of the silane with benzil at elevated temperature produced siladioxacyclopentene FcC(SiMe3)2{Si(OSiMe3)O2C2Ph2} (8).
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
10402 - Inorganic and nuclear chemistry
Result continuities
Project
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Continuities
S - Specificky vyzkum na vysokych skolach<br>I - Institucionalni podpora na dlouhodoby koncepcni rozvoj vyzkumne organizace
Others
Publication year
2025
Confidentiality
S - Úplné a pravdivé údaje o projektu nepodléhají ochraně podle zvláštních právních předpisů
Data specific for result type
Name of the periodical
Dalton Transactions
ISSN
1477-9226
e-ISSN
1477-9234
Volume of the periodical
54
Issue of the periodical within the volume
47
Country of publishing house
GB - UNITED KINGDOM
Number of pages
10
Pages from-to
17611-17620
UT code for WoS article
001613592600001
EID of the result in the Scopus database
2-s2.0-105023549783