Precise prediction of NMR chemical shifts in heavy transition-metal complexes (Pt, Ir, Au, Pd)

Kód výsledku v IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F00216224%3A14740%2F13%3A00066409" target="_blank" >RIV/00216224:14740/13:00066409 - isvavai.cz</a>

Výsledek na webu

<a href="http://www.smashnmr.org/" target="_blank" >http://www.smashnmr.org/</a>

DOI - Digital Object Identifier

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Jazyk výsledku

angličtina

Název v původním jazyce

Precise prediction of NMR chemical shifts in heavy transition-metal complexes (Pt, Ir, Au, Pd)

Popis výsledku v původním jazyce

We present a simple method for correct and precise NMR chemical shift prediction, employing the calibrated amount of exact-exchange admixture in hybrid GGA functionals (e.g., PBE0), which is routinely available in programs like ADF. The amount of exact-exchange admixture was carefully calibrated relative to experiment for platinum(IV) and iridium(III) octahedral complexes with adenine-based ligands [1] and further tested on square-planar platinum(II), palladium(II), and gold(III) complexes with pyridine-based ligands. In all cases the increased amount of exact exchange improved the agreement with experiment significantly not only for atoms directly bonded to and influenced by the heavy element (deviation of ~15 ppm dropped down to ~1-2 ppm) but virtually for all 13C and 15N NMR chemical shifts. Using this approach we are able to predict the 13C and 15N NMR chemical shifts with RMSDs from experiment of about 1-2 ppm (compared to RMSDs about ~4-7 ppm for standard GGA functionals). Refere

Název v anglickém jazyce

Precise prediction of NMR chemical shifts in heavy transition-metal complexes (Pt, Ir, Au, Pd)

Popis výsledku anglicky

We present a simple method for correct and precise NMR chemical shift prediction, employing the calibrated amount of exact-exchange admixture in hybrid GGA functionals (e.g., PBE0), which is routinely available in programs like ADF. The amount of exact-exchange admixture was carefully calibrated relative to experiment for platinum(IV) and iridium(III) octahedral complexes with adenine-based ligands [1] and further tested on square-planar platinum(II), palladium(II), and gold(III) complexes with pyridine-based ligands. In all cases the increased amount of exact exchange improved the agreement with experiment significantly not only for atoms directly bonded to and influenced by the heavy element (deviation of ~15 ppm dropped down to ~1-2 ppm) but virtually for all 13C and 15N NMR chemical shifts. Using this approach we are able to predict the 13C and 15N NMR chemical shifts with RMSDs from experiment of about 1-2 ppm (compared to RMSDs about ~4-7 ppm for standard GGA functionals). Refere

Druh

O - Ostatní výsledky

CEP obor

CF - Fyzikální chemie a teoretická chemie

OECD FORD obor

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Projekt

<a href="/cs/project/GAP206%2F12%2F0539" target="_blank" >GAP206/12/0539: Struktura a dynamika komplexů přechodných kovů a jejich interakce s kavitandy</a><br>

Návaznosti

P - Projekt vyzkumu a vyvoje financovany z verejnych zdroju (s odkazem do CEP)

Rok uplatnění

2013

Kód důvěrnosti údajů

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