Počet záznamů: 1
Nuclear Magnetic Shielding of Monoboranes: Calculation and Assessment of B-11 NMR Chemical Shifts in Planar BX3 and in Tetrahedral [BX4](-) Systems
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SYSNO ASEP 0484195 Druh ASEP J - Článek v odborném periodiku Zařazení RIV J - Článek v odborném periodiku Poddruh J Článek ve WOS Název Nuclear Magnetic Shielding of Monoboranes: Calculation and Assessment of B-11 NMR Chemical Shifts in Planar BX3 and in Tetrahedral [BX4](-) Systems Tvůrce(i) Macháček, Jan (UACH-T) RID, ORCID, SAI
Bühl, M. (GB)
Fanfrlík, Jindřich (UOCHB-X) RID, ORCID
Hnyk, Drahomír (UACH-T) SAI, RID, ORCIDZdroj.dok. Journal of Physical Chemistry A. - : American Chemical Society - ISSN 1089-5639
Roč. 121, č. 50 (2017), s. 9631-9637Poč.str. 7 s. Jazyk dok. eng - angličtina Země vyd. US - Spojené státy americké Klíč. slova Electrostatic potentials ; Nonrelativistic ; Nuclear magnetic shieldings Vědní obor RIV CA - Anorganická chemie Obor OECD Inorganic and nuclear chemistry CEP GA17-08045S GA ČR - Grantová agentura ČR Institucionální podpora UACH-T - RVO:61388980 ; UOCHB-X - RVO:61388963 UT WOS 000418783900008 EID SCOPUS 85038893731 DOI 10.1021/acs.jpca.7b09831 Anotace 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. Pracoviště Ústav anorganické chemie Kontakt Jana Kroneislová, krone@iic.cas.cz, Tel.: 311 236 931 Rok sběru 2018
Počet záznamů: 1