Synthesis, reactivity and coordination behaviour of a ferrocene phosphinostibine and intramolecular interactions in its P(V) and Sb(V) derivatives
Identifikátory výsledku
Kód výsledku v IS VaVaI
<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F00216208%3A11310%2F24%3A10479298" target="_blank" >RIV/00216208:11310/24:10479298 - isvavai.cz</a>
Výsledek na webu
<a href="https://verso.is.cuni.cz/pub/verso.fpl?fname=obd_publikace_handle&handle=PjGn12xqn4" target="_blank" >https://verso.is.cuni.cz/pub/verso.fpl?fname=obd_publikace_handle&handle=PjGn12xqn4</a>
DOI - Digital Object Identifier
<a href="http://dx.doi.org/10.1039/d4nj00349g" target="_blank" >10.1039/d4nj00349g</a>
Alternativní jazyky
Jazyk výsledku
angličtina
Název v původním jazyce
Synthesis, reactivity and coordination behaviour of a ferrocene phosphinostibine and intramolecular interactions in its P(V) and Sb(V) derivatives
Popis výsledku v původním jazyce
Compared to their P,N-analogues, compounds combining P and Sb substituents remain less common. This contribution describes the synthesis of a new ferrocene phosphinostibine, Cy2PfcSbPh2 (3; fc = ferrocene-1,1'-diyl, Cy = cyclohexyl), and its derivatives modified at the phosphine and stibine moieties, viz., Cy2P(E)fcSbPh2 (E = BH3, O, S, AuCl), Cy2P(E)fcSbCl2Ph2 (E = BH3, S, AuCl) and stiboranes Cy2P(E)fcSb(O2C6Cl4)Ph2 (E = void, BH3, O, S and AuCl). The increased Lewis acidity of the Sb atom in the catecholatostiboranes Cy2PfcSb(O2C6Cl4)Ph2 and Cy2P(O)fcSb(O2C6Cl4)Ph2 resulted in intramolecular P -> Sb and O -> Sb dative interactions, which were not detected for the respective parent stibines or even in Cy2P(S)fcSb(O2C6Cl4)Ph2. While the P -> Sb interaction in Cy2PfcSb(O2C6Cl4)Ph2 was stronger than that in the "all-phenyl" analogue Ph2PfcSb(O2C6Cl4)Ph2 due to the electron-donating effect of the cyclohexyl groups, the bonding situations in Cy2P(O)fcSb(O2C6Cl4)Ph2 and Ph2P(O)fcSb(O2C6Cl4)Ph2, where the substituent effect was only indirect, remained very similar according to DFT calculations. A coordination study with 3 resulted in isolation of phosphine ([AuCl(3-κP)]), P,Sb-bridging ([(μ(P,Sb)-3)(AuCl)2]), and P,Sb-chelate ([(arene)MCl(3-κ(2)P,Sb)]X, where (arene)M/X = (η(6)-p-cymene)Ru(II)/PF6, (η(5)-C5Me5)Rh(III)/Cl, and (η(5)-C5Me5)Rh(III)/PF6, and [MCl2(3-κ(2)P,Sb)], where M = Pd and Pt) complexes. For some of these compounds, structure determination revealed structural distortions suggesting weak intramolecular Cl-Sb interactions, which were confirmed by theoretical methods.
Název v anglickém jazyce
Synthesis, reactivity and coordination behaviour of a ferrocene phosphinostibine and intramolecular interactions in its P(V) and Sb(V) derivatives
Popis výsledku anglicky
Compared to their P,N-analogues, compounds combining P and Sb substituents remain less common. This contribution describes the synthesis of a new ferrocene phosphinostibine, Cy2PfcSbPh2 (3; fc = ferrocene-1,1'-diyl, Cy = cyclohexyl), and its derivatives modified at the phosphine and stibine moieties, viz., Cy2P(E)fcSbPh2 (E = BH3, O, S, AuCl), Cy2P(E)fcSbCl2Ph2 (E = BH3, S, AuCl) and stiboranes Cy2P(E)fcSb(O2C6Cl4)Ph2 (E = void, BH3, O, S and AuCl). The increased Lewis acidity of the Sb atom in the catecholatostiboranes Cy2PfcSb(O2C6Cl4)Ph2 and Cy2P(O)fcSb(O2C6Cl4)Ph2 resulted in intramolecular P -> Sb and O -> Sb dative interactions, which were not detected for the respective parent stibines or even in Cy2P(S)fcSb(O2C6Cl4)Ph2. While the P -> Sb interaction in Cy2PfcSb(O2C6Cl4)Ph2 was stronger than that in the "all-phenyl" analogue Ph2PfcSb(O2C6Cl4)Ph2 due to the electron-donating effect of the cyclohexyl groups, the bonding situations in Cy2P(O)fcSb(O2C6Cl4)Ph2 and Ph2P(O)fcSb(O2C6Cl4)Ph2, where the substituent effect was only indirect, remained very similar according to DFT calculations. A coordination study with 3 resulted in isolation of phosphine ([AuCl(3-κP)]), P,Sb-bridging ([(μ(P,Sb)-3)(AuCl)2]), and P,Sb-chelate ([(arene)MCl(3-κ(2)P,Sb)]X, where (arene)M/X = (η(6)-p-cymene)Ru(II)/PF6, (η(5)-C5Me5)Rh(III)/Cl, and (η(5)-C5Me5)Rh(III)/PF6, and [MCl2(3-κ(2)P,Sb)], where M = Pd and Pt) complexes. For some of these compounds, structure determination revealed structural distortions suggesting weak intramolecular Cl-Sb interactions, which were confirmed by theoretical methods.
Klasifikace
Druh
J<sub>imp</sub> - Článek v periodiku v databázi Web of Science
CEP obor
—
OECD FORD obor
10402 - Inorganic and nuclear chemistry
Návaznosti výsledku
Projekt
<a href="/cs/project/GA21-02316S" target="_blank" >GA21-02316S: Ferrocenové ligandy s Sb-donorovými skupinami</a><br>
Návaznosti
P - Projekt vyzkumu a vyvoje financovany z verejnych zdroju (s odkazem do CEP)
Ostatní
Rok uplatnění
2024
Kód důvěrnosti údajů
S - Úplné a pravdivé údaje o projektu nepodléhají ochraně podle zvláštních právních předpisů
Údaje specifické pro druh výsledku
Název periodika
New Journal of Chemistry
ISSN
1144-0546
e-ISSN
1369-9261
Svazek periodika
48
Číslo periodika v rámci svazku
12
Stát vydavatele periodika
GB - Spojené království Velké Británie a Severního Irska
Počet stran výsledku
14
Strana od-do
5107-"5119.cover"
Kód UT WoS článku
001177161800001
EID výsledku v databázi Scopus
2-s2.0-85186072294