Thiaboranes on Both Sides of the Icosahedral Barrier: Retaining and Breaking the Barrier with Carbon Functionalities

Kód výsledku v IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F00216275%3A25310%2F19%3A39915525" target="_blank" >RIV/00216275:25310/19:39915525 - isvavai.cz</a>

Nalezeny alternativní kódy

RIV/61388980:_____/19:00506139 RIV/61388963:_____/19:00506139

Výsledek na webu

<a href="https://onlinelibrary.wiley.com/doi/full/10.1002/cplu.201900115" target="_blank" >https://onlinelibrary.wiley.com/doi/full/10.1002/cplu.201900115</a>

DOI - Digital Object Identifier

<a href="http://dx.doi.org/10.1002/cplu.201900115" target="_blank" >10.1002/cplu.201900115</a>

Jazyk výsledku

angličtina

Název v původním jazyce

Thiaboranes on Both Sides of the Icosahedral Barrier: Retaining and Breaking the Barrier with Carbon Functionalities

Popis výsledku v původním jazyce

The concept of icosahedral barrier has been expanded from the chemistry of carbaboranes to the area of thiaboranes. Both representatives of this barrier, i. e., closo-1,2-C2B10H12 and closo-1-SB11H11, are similar in their electron distribution, which is dominated by positive charge in the midpoint of the C-C vector and on the sulfur atom with experimentally determined dipole moments of 4.50 D and 3.64 D, respectively. This is a driving force for their reactivity as exemplified by their reactions with different carbon functionalities. Icosahedral closo-1-SB11H11 reacts both with an electron sextet containing carbon (in the form of N-heterocyclic carbenes), reported earlier, and with methyl iodide with an electron octet on the carbon. The latter reaction provides hexamethylated thiaborane on the basis of methylation so far unknown in this area of heteroborane chemistry. The computations of the heat of formation (Delta H-f(298)) make it possible to estimate the height of the barrier as well as to propose closo-thiaboranes beyond the barrier. Eleven and twelve vertex thiaboranes with nido electron count are known experimentally for breaking the barrier. These computations also suggest that the larger nido-thiaboranes are promising candidates for the corresponding experimental availability, i. e., the Delta H-f(298) of a 13-vertex nido-thiaborane cluster has been computed to be more negative than that of the well-known nido-SB10H11- cluster (-6.7 and -5.6 kcal mol(-1) per vertex, respectively).

Název v anglickém jazyce

Thiaboranes on Both Sides of the Icosahedral Barrier: Retaining and Breaking the Barrier with Carbon Functionalities

Popis výsledku anglicky

The concept of icosahedral barrier has been expanded from the chemistry of carbaboranes to the area of thiaboranes. Both representatives of this barrier, i. e., closo-1,2-C2B10H12 and closo-1-SB11H11, are similar in their electron distribution, which is dominated by positive charge in the midpoint of the C-C vector and on the sulfur atom with experimentally determined dipole moments of 4.50 D and 3.64 D, respectively. This is a driving force for their reactivity as exemplified by their reactions with different carbon functionalities. Icosahedral closo-1-SB11H11 reacts both with an electron sextet containing carbon (in the form of N-heterocyclic carbenes), reported earlier, and with methyl iodide with an electron octet on the carbon. The latter reaction provides hexamethylated thiaborane on the basis of methylation so far unknown in this area of heteroborane chemistry. The computations of the heat of formation (Delta H-f(298)) make it possible to estimate the height of the barrier as well as to propose closo-thiaboranes beyond the barrier. Eleven and twelve vertex thiaboranes with nido electron count are known experimentally for breaking the barrier. These computations also suggest that the larger nido-thiaboranes are promising candidates for the corresponding experimental availability, i. e., the Delta H-f(298) of a 13-vertex nido-thiaborane cluster has been computed to be more negative than that of the well-known nido-SB10H11- cluster (-6.7 and -5.6 kcal mol(-1) per vertex, respectively).

Druh

J_imp - Článek v periodiku v databázi Web of Science

CEP obor

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OECD FORD obor

10402 - Inorganic and nuclear chemistry

Projekt

<a href="/cs/project/GA17-08045S" target="_blank" >GA17-08045S: Vzájemně zesílené interakce mezi anorganickými a organickými systémy: krystalové uspořádání exo-substituovaných heteroboranů a jejich aduktů</a><br>

Návaznosti

P - Projekt vyzkumu a vyvoje financovany z verejnych zdroju (s odkazem do CEP)

Rok uplatnění

2019

Kód důvěrnosti údajů

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

Název periodika

ChemPlusChem

ISSN

2192-6506

e-ISSN

—

Svazek periodika

84

Číslo periodika v rámci svazku

7

Stát vydavatele periodika

DE - Spolková republika Německo

Počet stran výsledku

6

Strana od-do

822-827

Kód UT WoS článku

000477962500009

EID výsledku v databázi Scopus

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