Intramolecular Interactions between the Pnictogen Groups in a Rigid Ferrocene Phosphinostibine and the Corresponding Phosphine Chalcogenides, Stiboranes, and Their Complexes

Kód výsledku v IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F00216208%3A11310%2F25%3A10500609" target="_blank" >RIV/00216208:11310/25:10500609 - isvavai.cz</a>

Výsledek na webu

<a href="https://verso.is.cuni.cz/pub/verso.fpl?fname=obd_publikace_handle&handle=4RjmqVJ6TD" target="_blank" >https://verso.is.cuni.cz/pub/verso.fpl?fname=obd_publikace_handle&handle=4RjmqVJ6TD</a>

DOI - Digital Object Identifier

<a href="http://dx.doi.org/10.1021/acs.inorgchem.5c01332" target="_blank" >10.1021/acs.inorgchem.5c01332</a>

Jazyk výsledku

angličtina

Název v původním jazyce

Intramolecular Interactions between the Pnictogen Groups in a Rigid Ferrocene Phosphinostibine and the Corresponding Phosphine Chalcogenides, Stiboranes, and Their Complexes

Popis výsledku v původním jazyce

Differences in the chemical properties of phosphorus and antimony enable the synthesis of heteroditopic derivatives whose properties can be modified by altering the pnictogen substituents. In this work, 1-(diphenylstibino)-2-(dicyclohexylphosphino)ferrocene, [Fe(η(5)-1-Ph2Sb-2-Cy2PC5H3)(η(5)-C5H5)] (1), and the corresponding phosphine chalcogenides [Fe(η(5)-1-Ph2Sb-2-Cy2P(E)C5H3)(η(5)-C5H5)] (E = O, S, Se) and catecholatostiboranes [Fe(η(5)-1-Ph2(Cl4C6O2)Sb-2-Cy2P(E)C5H3)(η(5)-C5H5)] (E = void, O, S, Se) were examined, with a focus on the intramolecular donor-acceptor interactions between the antimony and the phosphorus substituents. Experimental data and theoretical analysis consistently indicated that these interactions can be described as pnictogen bonding between the Lewis acidic antimony and the lone pair at the phosphorus substituent (either at the phosphorus or at the chalcogen atom) and that they are significantly stronger in the stiboranes due to the increased Lewis acidity of the Sb atom. Noncovalent interactions were also observed in the chlorogold(I) complexes obtained from 1 and catecholatostiborane [Fe(η(5)-1-Ph2(Cl4C6O2)Sb-2-Cy2PC5H3)(η(5)-C5H5)] as P-donors. As shown by experiments in Au-mediated cyclization of N-propargylbenzamide, the noncoordinated antimony group influenced the catalytic properties of the Au(I) complexes. Notably, an intramolecular Cl -&gt; Sb pnictogen bond affected the molecular geometry of the Pd(II) complex [PdCl2(1-κ(2)P,Sb)], which in turn suggested that the structural influence exerted by ligands of this type needs to be assessed with care.

Název v anglickém jazyce

Intramolecular Interactions between the Pnictogen Groups in a Rigid Ferrocene Phosphinostibine and the Corresponding Phosphine Chalcogenides, Stiboranes, and Their Complexes

Popis výsledku anglicky

Differences in the chemical properties of phosphorus and antimony enable the synthesis of heteroditopic derivatives whose properties can be modified by altering the pnictogen substituents. In this work, 1-(diphenylstibino)-2-(dicyclohexylphosphino)ferrocene, [Fe(η(5)-1-Ph2Sb-2-Cy2PC5H3)(η(5)-C5H5)] (1), and the corresponding phosphine chalcogenides [Fe(η(5)-1-Ph2Sb-2-Cy2P(E)C5H3)(η(5)-C5H5)] (E = O, S, Se) and catecholatostiboranes [Fe(η(5)-1-Ph2(Cl4C6O2)Sb-2-Cy2P(E)C5H3)(η(5)-C5H5)] (E = void, O, S, Se) were examined, with a focus on the intramolecular donor-acceptor interactions between the antimony and the phosphorus substituents. Experimental data and theoretical analysis consistently indicated that these interactions can be described as pnictogen bonding between the Lewis acidic antimony and the lone pair at the phosphorus substituent (either at the phosphorus or at the chalcogen atom) and that they are significantly stronger in the stiboranes due to the increased Lewis acidity of the Sb atom. Noncovalent interactions were also observed in the chlorogold(I) complexes obtained from 1 and catecholatostiborane [Fe(η(5)-1-Ph2(Cl4C6O2)Sb-2-Cy2PC5H3)(η(5)-C5H5)] as P-donors. As shown by experiments in Au-mediated cyclization of N-propargylbenzamide, the noncoordinated antimony group influenced the catalytic properties of the Au(I) complexes. Notably, an intramolecular Cl -&gt; Sb pnictogen bond affected the molecular geometry of the Pd(II) complex [PdCl2(1-κ(2)P,Sb)], which in turn suggested that the structural influence exerted by ligands of this type needs to be assessed with care.

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

Inorganic Chemistry

ISSN

0020-1669

e-ISSN

1520-510X

Svazek periodika

64

Číslo periodika v rámci svazku

22

Stát vydavatele periodika

US - Spojené státy americké

Počet stran výsledku

18

Strana od-do

11075-11092

Kód UT WoS článku

001494633000001

EID výsledku v databázi Scopus

2-s2.0-105005938488