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

Result code in 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>

Alternative codes found

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

Result on the web

<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>

Result language

angličtina

Original language name

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

Original language description

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.

Czech name

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Czech description

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Type

J_imp - Article in a specialist periodical, which is included in the Web of Science database

CEP classification

—

OECD FORD branch

10402 - Inorganic and nuclear chemistry

Project

<a href="/en/project/TH01020844" target="_blank" >TH01020844: Cluster borate anion technology for new materials in medicine and electronics</a><br>

Continuities

I - Institucionalni podpora na dlouhodoby koncepcni rozvoj vyzkumne organizace

Publication year

2018

Confidentiality

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

Name of the periodical

Journal of Organometallic Chemistry

ISSN

0022-328X

e-ISSN

—

Volume of the periodical

865

Issue of the periodical within the volume

1

Country of publishing house

NL - THE KINGDOM OF THE NETHERLANDS

Number of pages

11

Pages from-to

189-199

UT code for WoS article

000432599400028

EID of the result in the Scopus database

2-s2.0-85044008604