Nuclear Magnetic Shielding of Monoboranes: Calculation and Assessment of B-11 NMR Chemical Shifts in Planar BX3 and in Tetrahedral [BX4](-) Systems

Kód výsledku v IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F61388963%3A_____%2F17%3A00484195" target="_blank" >RIV/61388963:_____/17:00484195 - isvavai.cz</a>

Nalezeny alternativní kódy

RIV/61388980:_____/17:00484195

Výsledek na webu

<a href="http://dx.doi.org/10.1021/acs.jpca.7b09831" target="_blank" >http://dx.doi.org/10.1021/acs.jpca.7b09831</a>

DOI - Digital Object Identifier

<a href="http://dx.doi.org/10.1021/acs.jpca.7b09831" target="_blank" >10.1021/acs.jpca.7b09831</a>

Jazyk výsledku

angličtina

Název v původním jazyce

Nuclear Magnetic Shielding of Monoboranes: Calculation and Assessment of B-11 NMR Chemical Shifts in Planar BX3 and in Tetrahedral [BX4](-) Systems

Popis výsledku v původním jazyce

B-11 NMR chemical shifts of tricoordinated BX3 and tetracoordinated BX4- compounds (X = H, CH3, F, Cl, Br, I, OH, SH, NH2, and CH=CH2) were computed, and the shielding tensors were explored not only within the non relativistic GIAO approach but also by application of both relativistic ZORA computations including spin orbit coupling as well as scalar nonrelativistic ZORA computations (BP86 level of density functional theory). The contributions of the spin orbit coupling to the overall shieldings are decisive for X = Br and I in both series. No relationship was found between the 2p orbital occupancies or 1/Delta E (difference between LUMO and suitably occupied MO that can be coupled with LUMO) with the shielding tensors (or their principal values) in the BX3 series. However, a multidimensional statistical approach known as factor analysis (frequently used in chemometrics) revealed that three factors account for 92% of the cumulative proportion of total variance. The main components of the first factor are occupancies in the 2p(x) and 2p(y)), orbitals and 1/Delta E, the second factor is mainly the occupancy in the 2p(z) orbital and the inductive substituent parameters by Taft. Finally, the third factor consists exclusively (98.4%) of the electrostatic potential (V-max), which is directly related to the so-called pi-hole magnitudes.

Název v anglickém jazyce

Nuclear Magnetic Shielding of Monoboranes: Calculation and Assessment of B-11 NMR Chemical Shifts in Planar BX3 and in Tetrahedral [BX4](-) Systems

Popis výsledku anglicky

B-11 NMR chemical shifts of tricoordinated BX3 and tetracoordinated BX4- compounds (X = H, CH3, F, Cl, Br, I, OH, SH, NH2, and CH=CH2) were computed, and the shielding tensors were explored not only within the non relativistic GIAO approach but also by application of both relativistic ZORA computations including spin orbit coupling as well as scalar nonrelativistic ZORA computations (BP86 level of density functional theory). The contributions of the spin orbit coupling to the overall shieldings are decisive for X = Br and I in both series. No relationship was found between the 2p orbital occupancies or 1/Delta E (difference between LUMO and suitably occupied MO that can be coupled with LUMO) with the shielding tensors (or their principal values) in the BX3 series. However, a multidimensional statistical approach known as factor analysis (frequently used in chemometrics) revealed that three factors account for 92% of the cumulative proportion of total variance. The main components of the first factor are occupancies in the 2p(x) and 2p(y)), orbitals and 1/Delta E, the second factor is mainly the occupancy in the 2p(z) orbital and the inductive substituent parameters by Taft. Finally, the third factor consists exclusively (98.4%) of the electrostatic potential (V-max), which is directly related to the so-called pi-hole magnitudes.

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/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

2017

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

121

Číslo periodika v rámci svazku

50

Stát vydavatele periodika

US - Spojené státy americké

Počet stran výsledku

7

Strana od-do

9631-9637

Kód UT WoS článku

000418783900008

EID výsledku v databázi Scopus

2-s2.0-85038893731