Beyond the Limits of Perbromo-Substituted Octahedral Pnictogenaboranes: A Spectroscopic and Computational Study

Kód výsledku v IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F61388963%3A_____%2F24%3A00585093" target="_blank" >RIV/61388963:_____/24:00585093 - isvavai.cz</a>

Nalezeny alternativní kódy

RIV/61388980:_____/24:00585093

Výsledek na webu

<a href="https://doi.org/10.1002/ejic.202400053" target="_blank" >https://doi.org/10.1002/ejic.202400053</a>

DOI - Digital Object Identifier

<a href="http://dx.doi.org/10.1002/ejic.202400053" target="_blank" >10.1002/ejic.202400053</a>

Jazyk výsledku

angličtina

Název v původním jazyce

Beyond the Limits of Perbromo-Substituted Octahedral Pnictogenaboranes: A Spectroscopic and Computational Study

Popis výsledku v původním jazyce

Octahedral closo-1,2-Pn2B4Br4 (Pn=P, As) molecules react with tetrahydrothiophene (THT), regarded as a soft base, much slower than with tetrahydrofuran (THF), considered a hard base. Namely, the reaction begins with only Pn=P at temperatures above 140 degrees C, 4-Br(CH2)4S-closo-1,2-P2B4Br3 has been detected as the first product resulting from the cleavage and insertion of a thiobutylate group into the B-Br bond. Unlike in the reaction with THF, the addition of a second THT moiety has not been observed. Conversely, also starting from 140 degrees C, conjuncto-3,3'-(1,2-Pn2B4Br3)2 has been found as the final product of the reaction, which indicates the presence of 3-Br(CH2)4S-closo-1,2-P2B4Br3 as another intermediate during the conversion. A computational examination has revealed that it occurs through a pentagonal pyramidal stationary point as an additional intermediate, the latter of which serves as the crucial structural assembly for the thermal conversion that produces the conjuncto motif. Computations of the energy balance and 11B and 31P NMR chemical shifts are in agreement with experimental observations. This reaction is made possible by the presence of sigma-holes on the bromine atoms. In addition, the presence of the sigma-holes on the pnictogens has enabled ESI-MS to detect various anions appearing during earlier and current syntheses.

Název v anglickém jazyce

Beyond the Limits of Perbromo-Substituted Octahedral Pnictogenaboranes: A Spectroscopic and Computational Study

Popis výsledku anglicky

Octahedral closo-1,2-Pn2B4Br4 (Pn=P, As) molecules react with tetrahydrothiophene (THT), regarded as a soft base, much slower than with tetrahydrofuran (THF), considered a hard base. Namely, the reaction begins with only Pn=P at temperatures above 140 degrees C, 4-Br(CH2)4S-closo-1,2-P2B4Br3 has been detected as the first product resulting from the cleavage and insertion of a thiobutylate group into the B-Br bond. Unlike in the reaction with THF, the addition of a second THT moiety has not been observed. Conversely, also starting from 140 degrees C, conjuncto-3,3'-(1,2-Pn2B4Br3)2 has been found as the final product of the reaction, which indicates the presence of 3-Br(CH2)4S-closo-1,2-P2B4Br3 as another intermediate during the conversion. A computational examination has revealed that it occurs through a pentagonal pyramidal stationary point as an additional intermediate, the latter of which serves as the crucial structural assembly for the thermal conversion that produces the conjuncto motif. Computations of the energy balance and 11B and 31P NMR chemical shifts are in agreement with experimental observations. This reaction is made possible by the presence of sigma-holes on the bromine atoms. In addition, the presence of the sigma-holes on the pnictogens has enabled ESI-MS to detect various anions appearing during earlier and current syntheses.

Druh

J_imp - Článek v periodiku v databázi Web of Science

CEP obor

—

OECD FORD obor

10402 - Inorganic and nuclear chemistry

Projekt

<a href="/cs/project/GA19-17156S" target="_blank" >GA19-17156S: Chemie globulárních uhlovodíků s B-klastrovým jádrem uvnitř methylovaného obalu</a><br>

Návaznosti

I - Institucionalni podpora na dlouhodoby koncepcni rozvoj vyzkumne organizace

Rok uplatnění

2024

Kód důvěrnosti údajů

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

Název periodika

European Journal of Inorganic Chemistry

ISSN

1434-1948

e-ISSN

1099-0682

Svazek periodika

27

Číslo periodika v rámci svazku

17

Stát vydavatele periodika

US - Spojené státy americké

Počet stran výsledku

7

Strana od-do

e202400053

Kód UT WoS článku

001186873300001

EID výsledku v databázi Scopus

2-s2.0-85188173583