Transmission of Electronic Substituent Effects across the 1,12-Dicarba-doso-dodecaborane Cage: A Computational Study Based on Structural Variation, Atomic Charges, and C-13 NMR Chemical Shifts

Kód výsledku v IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F61388980%3A_____%2F15%3A00442459" target="_blank" >RIV/61388980:_____/15:00442459 - isvavai.cz</a>

Výsledek na webu

<a href="http://dx.doi.org/10.1021/jp5106407" target="_blank" >http://dx.doi.org/10.1021/jp5106407</a>

DOI - Digital Object Identifier

<a href="http://dx.doi.org/10.1021/jp5106407" target="_blank" >10.1021/jp5106407</a>

Jazyk výsledku

angličtina

Název v původním jazyce

Transmission of Electronic Substituent Effects across the 1,12-Dicarba-doso-dodecaborane Cage: A Computational Study Based on Structural Variation, Atomic Charges, and C-13 NMR Chemical Shifts

Popis výsledku v původním jazyce

The ability of the 1,12-dicarba-closo-dodecaborane cage to transmit long-range substituent effects has been investigated by analyzing the structural variation of a phenyl probe bonded to C1, as caused by a remote substituent X at C12. The geometries of 41 Ph-CB10H10C-X molecules, including 11 charged species, have been determined by MO calculations at the B3LYP/6-311++G** level of theory. The structural variation of the phenyl probe is best represented by a linear combination of the internal ring angles, termed S-F(CARB). Multiple regression analysis of S-F(CARB), using appropriate explanatory variables, reveals the presence of resonance effects, superimposed onto the field effect of the remote substituent. The ability of the para-carborane cage to transmit resonance effects is, on average, about one-half of that of the para-phenylene frame in coplanar para-substituted biphenyls. Analysis of the pi-charge variation of the phenyl probe confirms that the para-carborane frame is less capa

Název v anglickém jazyce

Transmission of Electronic Substituent Effects across the 1,12-Dicarba-doso-dodecaborane Cage: A Computational Study Based on Structural Variation, Atomic Charges, and C-13 NMR Chemical Shifts

Popis výsledku anglicky

The ability of the 1,12-dicarba-closo-dodecaborane cage to transmit long-range substituent effects has been investigated by analyzing the structural variation of a phenyl probe bonded to C1, as caused by a remote substituent X at C12. The geometries of 41 Ph-CB10H10C-X molecules, including 11 charged species, have been determined by MO calculations at the B3LYP/6-311++G** level of theory. The structural variation of the phenyl probe is best represented by a linear combination of the internal ring angles, termed S-F(CARB). Multiple regression analysis of S-F(CARB), using appropriate explanatory variables, reveals the presence of resonance effects, superimposed onto the field effect of the remote substituent. The ability of the para-carborane cage to transmit resonance effects is, on average, about one-half of that of the para-phenylene frame in coplanar para-substituted biphenyls. Analysis of the pi-charge variation of the phenyl probe confirms that the para-carborane frame is less capa

Druh

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

CEP obor

CA - Anorganická chemie

OECD FORD obor

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Projekt

<a href="/cs/project/GAP208%2F10%2F2269" target="_blank" >GAP208/10/2269: Vývoj a strukturní charateristika možných prekursorů borových nanotrubic na bázi spojených ikosahedronů. Sdílené ikosahedrony kovem.</a><br>

Návaznosti

I - Institucionalni podpora na dlouhodoby koncepcni rozvoj vyzkumne organizace

Rok uplatnění

2015

Kód důvěrnosti údajů

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

Název periodika

Journal of Physical Chemistry A

ISSN

1089-5639

e-ISSN

—

Svazek periodika

119

Číslo periodika v rámci svazku

1

Stát vydavatele periodika

US - Spojené státy americké

Počet stran výsledku

10

Strana od-do

205-214

Kód UT WoS článku

000347743800023

EID výsledku v databázi Scopus

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