Synthesis, structure, photochemical and electrochemical properties of α-germyl ferrocenyl ketones

Kód výsledku v 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>

Výsledek na webu

<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>

Jazyk výsledku

angličtina

Název v původním jazyce

Synthesis, structure, photochemical and electrochemical properties of α-germyl ferrocenyl ketones

Popis výsledku v původním jazyce

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).

Název v anglickém jazyce

Synthesis, structure, photochemical and electrochemical properties of α-germyl ferrocenyl ketones

Popis výsledku anglicky

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).

Druh

J_imp - Článek v periodiku v databázi Web of Science

CEP obor

—

OECD FORD obor

10402 - Inorganic and nuclear chemistry

Projekt

—

Návaznosti

S - Specificky vyzkum na vysokych skolach<br>I - Institucionalni podpora na dlouhodoby koncepcni rozvoj vyzkumne organizace

Rok uplatnění

2025

Kód důvěrnosti údajů

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

Název periodika

Dalton Transactions

ISSN

1477-9226

e-ISSN

1477-9234

Svazek periodika

54

Číslo periodika v rámci svazku

47

Stát vydavatele periodika

GB - Spojené království Velké Británie a Severního Irska

Počet stran výsledku

10

Strana od-do

17611-17620

Kód UT WoS článku

001613592600001

EID výsledku v databázi Scopus

2-s2.0-105023549783