Synthesis and selected properties of nonahalogenated 2-ammonio-decaborate anions and their derivatives substituted at N-centre

Kód výsledku v IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F00216275%3A25310%2F18%3A39913263" target="_blank" >RIV/00216275:25310/18:39913263 - isvavai.cz</a>

Nalezeny alternativní kódy

RIV/68081707:_____/18:00488749 RIV/61388980:_____/18:00488749 RIV/61388963:_____/18:00488749

Výsledek na webu

<a href="http://10.1016/j.jorganchem.2018.02.050" target="_blank" >http://10.1016/j.jorganchem.2018.02.050</a>

DOI - Digital Object Identifier

<a href="http://dx.doi.org/10.1016/j.jorganchem.2018.02.050" target="_blank" >10.1016/j.jorganchem.2018.02.050</a>

Jazyk výsledku

angličtina

Název v původním jazyce

Synthesis and selected properties of nonahalogenated 2-ammonio-decaborate anions and their derivatives substituted at N-centre

Popis výsledku v původním jazyce

New preparative methods for halogenation of the cage producing the corresponding [2-NH3-B10X9]species (2(-) to 4(-), X = Cl, Br, I) have been developed using halogenations by elemental halogens in a glass pressure vessel. Compared to similar icosahedral species of formulation [1-H3N-B12X11](-) (X = Cl, Br), the N-alkylation reactions in 10-vertex series proceed significantly more easily. The reason for this difference is conceivably due to the two orders of magnitude lower basicity of the amino group, with pKa values in the interval from 9.27 to 8.37, and slightly lower steric strain around the reaction centre. Thus methylations with MeI under mild conditions provided the whole series of corresponding quarternary amines of the formulation [2-Me3N-B10X9](-)(5(-) to 7(-), X = Cl, Br, I). The effect of the steric strain of the surrounding halogens on the reactivity at the NH3-centre could then be better seen from reactions with bulkier benzyl bromide. Under comparable conditions, these reactions resulted in the ready formation of disubstituted compounds in case of X = Cl (8(-)), mixture of mono and disubstituted derivatives for X = Br (9(-), 10(-)) or in monosubstited product for X = I (11(-)) only. Dibenzyl derivative of the nonaiodinated products (12(-)) could be still obtained, however only under more forcing conditions. The single-crystal Xray diffraction structures of all three polyhalogenated derivatives 2(-) to 4(-) are presented along with that for benzyl derivative 10(-), spectral and physicochemical properties of these polyhalogenated systems are outlined along with specific insights into specific properties of the NH3 group.

Název v anglickém jazyce

Synthesis and selected properties of nonahalogenated 2-ammonio-decaborate anions and their derivatives substituted at N-centre

Popis výsledku anglicky

New preparative methods for halogenation of the cage producing the corresponding [2-NH3-B10X9]species (2(-) to 4(-), X = Cl, Br, I) have been developed using halogenations by elemental halogens in a glass pressure vessel. Compared to similar icosahedral species of formulation [1-H3N-B12X11](-) (X = Cl, Br), the N-alkylation reactions in 10-vertex series proceed significantly more easily. The reason for this difference is conceivably due to the two orders of magnitude lower basicity of the amino group, with pKa values in the interval from 9.27 to 8.37, and slightly lower steric strain around the reaction centre. Thus methylations with MeI under mild conditions provided the whole series of corresponding quarternary amines of the formulation [2-Me3N-B10X9](-)(5(-) to 7(-), X = Cl, Br, I). The effect of the steric strain of the surrounding halogens on the reactivity at the NH3-centre could then be better seen from reactions with bulkier benzyl bromide. Under comparable conditions, these reactions resulted in the ready formation of disubstituted compounds in case of X = Cl (8(-)), mixture of mono and disubstituted derivatives for X = Br (9(-), 10(-)) or in monosubstited product for X = I (11(-)) only. Dibenzyl derivative of the nonaiodinated products (12(-)) could be still obtained, however only under more forcing conditions. The single-crystal Xray diffraction structures of all three polyhalogenated derivatives 2(-) to 4(-) are presented along with that for benzyl derivative 10(-), spectral and physicochemical properties of these polyhalogenated systems are outlined along with specific insights into specific properties of the NH3 group.

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/TH01020844" target="_blank" >TH01020844: Technologie klastrových boratových aniontů pro nové materiály a aplikace v medicíně a elektrotechnice</a><br>

Návaznosti

I - Institucionalni podpora na dlouhodoby koncepcni rozvoj vyzkumne organizace

Rok uplatnění

2018

Kód důvěrnosti údajů

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

Název periodika

Journal of Organometallic Chemistry

ISSN

0022-328X

e-ISSN

—

Svazek periodika

865

Číslo periodika v rámci svazku

1

Stát vydavatele periodika

NL - Nizozemsko

Počet stran výsledku

11

Strana od-do

189-199

Kód UT WoS článku

000432599400028

EID výsledku v databázi Scopus

2-s2.0-85044008604