Prototropic mu-H-8,H-9 and mu-H-9,H-10 Tautomers Derived from the [nido-5,6-C2B8H11](-) Anion

Kód výsledku v IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F61388980%3A_____%2F16%3A00466309" target="_blank" >RIV/61388980:_____/16:00466309 - isvavai.cz</a>

Výsledek na webu

<a href="http://dx.doi.org/10.1021/acs.inorgchem.6b02076" target="_blank" >http://dx.doi.org/10.1021/acs.inorgchem.6b02076</a>

DOI - Digital Object Identifier

<a href="http://dx.doi.org/10.1021/acs.inorgchem.6b02076" target="_blank" >10.1021/acs.inorgchem.6b02076</a>

Jazyk výsledku

angličtina

Název v původním jazyce

Prototropic mu-H-8,H-9 and mu-H-9,H-10 Tautomers Derived from the [nido-5,6-C2B8H11](-) Anion

Popis výsledku v původním jazyce

Reported is an unusual tautomeric behavior within the [nido-5,6-C2B8H11](-) (1a(-)) cage that has no precedence in the whole area of carborane chemistry. Isolated were two skeletal tautomers, anions [6-Ph-nido-5,6-C2B8H10-mu(8,9)](-) (2d(-)) and [5,6-Me-2-nido-5,6-C2B8H9-mu(9,10)](-) (3b(-)), which differ in the positioning of the open face hydrogen bridge. Their structures have been determined by X-ray diffraction analyses. The 3b(-) structure is stabilized by intermolecular interaction involving Et3NH+ and B8-B9 and H8 atoms in the solid phase; however, its dissolution in CD3CN causes instant conversion to the more stable [5,6-Me-2-nido-5,6-C2B8H9-mu(8,9)](-) (2b(-)) tautomer. The dynamic electron-correlation-based MP2/6-31G* computations suggest that the parent [nido-5,6-C2B8H11-mu(8,9)](-) (2a(-)) tautomer is 3.9 kcal center dot mol(-1) more stable than the [nido-5,6-C2B8H11-mu(9,10)](-) (3a(-)) counterpart and the mu(8,9) structure 2(-) is therefore the most stable tautomeric form in the solution, as was also demonstrated by multinuclear (H-1, B-11, and C-13) NMR measurements on the whole series of C-substituted compounds.

Název v anglickém jazyce

Prototropic mu-H-8,H-9 and mu-H-9,H-10 Tautomers Derived from the [nido-5,6-C2B8H11](-) Anion

Popis výsledku anglicky

Reported is an unusual tautomeric behavior within the [nido-5,6-C2B8H11](-) (1a(-)) cage that has no precedence in the whole area of carborane chemistry. Isolated were two skeletal tautomers, anions [6-Ph-nido-5,6-C2B8H10-mu(8,9)](-) (2d(-)) and [5,6-Me-2-nido-5,6-C2B8H9-mu(9,10)](-) (3b(-)), which differ in the positioning of the open face hydrogen bridge. Their structures have been determined by X-ray diffraction analyses. The 3b(-) structure is stabilized by intermolecular interaction involving Et3NH+ and B8-B9 and H8 atoms in the solid phase; however, its dissolution in CD3CN causes instant conversion to the more stable [5,6-Me-2-nido-5,6-C2B8H9-mu(8,9)](-) (2b(-)) tautomer. The dynamic electron-correlation-based MP2/6-31G* computations suggest that the parent [nido-5,6-C2B8H11-mu(8,9)](-) (2a(-)) tautomer is 3.9 kcal center dot mol(-1) more stable than the [nido-5,6-C2B8H11-mu(9,10)](-) (3a(-)) counterpart and the mu(8,9) structure 2(-) is therefore the most stable tautomeric form in the solution, as was also demonstrated by multinuclear (H-1, B-11, and C-13) NMR measurements on the whole series of C-substituted compounds.

Druh

J_x - Nezařazeno - Článek v odborném periodiku (Jimp, Jsc a Jost)

CEP obor

CA - Anorganická chemie

OECD FORD obor

—

Projekt

<a href="/cs/project/GA16-01618S" target="_blank" >GA16-01618S: Desetivrcholové dikarbaboranové molekulární útvary vytvořené alkylací</a><br>

Návaznosti

I - Institucionalni podpora na dlouhodoby koncepcni rozvoj vyzkumne organizace

Rok uplatnění

2016

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

—

Svazek periodika

55

Číslo periodika v rámci svazku

20

Stát vydavatele periodika

US - Spojené státy americké

Počet stran výsledku

3

Strana od-do

10122-10124

Kód UT WoS článku

000385785700024

EID výsledku v databázi Scopus

2-s2.0-84992130154