Palladium(II) and Platinum(II) Bis(Stibinidene) Complexes with Intramolecular Hydrogen-Bond Enforced Geometries

Kód výsledku v IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F00216275%3A25310%2F24%3A39922147" target="_blank" >RIV/00216275:25310/24:39922147 - isvavai.cz</a>

Výsledek na webu

<a href="https://chemistry-europe.onlinelibrary.wiley.com/doi/10.1002/cplu.202300573" target="_blank" >https://chemistry-europe.onlinelibrary.wiley.com/doi/10.1002/cplu.202300573</a>

DOI - Digital Object Identifier

<a href="http://dx.doi.org/10.1002/cplu.202300573" target="_blank" >10.1002/cplu.202300573</a>

Jazyk výsledku

angličtina

Název v původním jazyce

Palladium(II) and Platinum(II) Bis(Stibinidene) Complexes with Intramolecular Hydrogen-Bond Enforced Geometries

Popis výsledku v původním jazyce

The coordination capability of two N,C,N pincer coordinated stibinidenes, i. e. bis(imino)- [2,6-(DippN=CH)2C6H3]Sb (1) or imino-amino- [2-(DippN=CH)-6-(DippNHCH2)C6H3]Sb (2) toward palladium(II) and platinum(II) centers was examined. In the course of this study, seven new square-planar bis(stibinidene) complexes were synthesized and characterized by NMR, IR, Raman, UV-vis spectroscopy and single crystal (sc)-X-ray diffraction analysis. In all cases, both stibinidene ligands 1 or 2 adopt trans positions, but differ significantly in the torsion angle describing mutual orientation of aromatic rings of the stibinidenes along the Sb-Pd/Pt-Sb axes. Furthermore, majority of complexes form isomers in solution most probably due to a hindered rotation around Sb-Pd/Pt bonds caused by bulkiness of 1 and 2. This phenomenon also seems to be influenced by the absence/presence of a pendant -CH2NH- group in 1/2 that is able to form intramolecular hydrogen bonds with the adjacent chlorine atom(s) attached to the metal centers. The whole problem was subjected to a theoretical study focusing on the role of hydrogen bonds in structure architecture of the complexes. To describe the UV-vis spectra of these highly coloured complexes, TD-DFT calculations were employed. These outline differences between the stibinidene ligands, the transition metals as well as between the charge of the complexes (neutral or anionic). The coordination capability of two N,C,N pincer chelated stibinidenes (1 and 2) toward palladium(II) and platinum(II) centres is reported. This study reveals significant structural differences between these ligands caused mainly by the formation of hydrogen bonds via pendant NH groups of 2.image

Název v anglickém jazyce

Palladium(II) and Platinum(II) Bis(Stibinidene) Complexes with Intramolecular Hydrogen-Bond Enforced Geometries

Popis výsledku anglicky

The coordination capability of two N,C,N pincer coordinated stibinidenes, i. e. bis(imino)- [2,6-(DippN=CH)2C6H3]Sb (1) or imino-amino- [2-(DippN=CH)-6-(DippNHCH2)C6H3]Sb (2) toward palladium(II) and platinum(II) centers was examined. In the course of this study, seven new square-planar bis(stibinidene) complexes were synthesized and characterized by NMR, IR, Raman, UV-vis spectroscopy and single crystal (sc)-X-ray diffraction analysis. In all cases, both stibinidene ligands 1 or 2 adopt trans positions, but differ significantly in the torsion angle describing mutual orientation of aromatic rings of the stibinidenes along the Sb-Pd/Pt-Sb axes. Furthermore, majority of complexes form isomers in solution most probably due to a hindered rotation around Sb-Pd/Pt bonds caused by bulkiness of 1 and 2. This phenomenon also seems to be influenced by the absence/presence of a pendant -CH2NH- group in 1/2 that is able to form intramolecular hydrogen bonds with the adjacent chlorine atom(s) attached to the metal centers. The whole problem was subjected to a theoretical study focusing on the role of hydrogen bonds in structure architecture of the complexes. To describe the UV-vis spectra of these highly coloured complexes, TD-DFT calculations were employed. These outline differences between the stibinidene ligands, the transition metals as well as between the charge of the complexes (neutral or anionic). The coordination capability of two N,C,N pincer chelated stibinidenes (1 and 2) toward palladium(II) and platinum(II) centres is reported. This study reveals significant structural differences between these ligands caused mainly by the formation of hydrogen bonds via pendant NH groups of 2.image

Druh

J_imp - Článek v periodiku v databázi Web of Science

CEP obor

—

OECD FORD obor

10400 - Chemical sciences

Projekt

<a href="/cs/project/GA21-02964S" target="_blank" >GA21-02964S: Dusíkaté ligandy pro prvky nepřechodných kovů - objemnější, konjugovanější a reaktivnější</a><br>

Návaznosti

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

Rok uplatnění

2024

Kód důvěrnosti údajů

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

Název periodika

ChemPlusChem

ISSN

2192-6506

e-ISSN

2192-6506

Svazek periodika

89

Číslo periodika v rámci svazku

5

Stát vydavatele periodika

DE - Spolková republika Německo

Počet stran výsledku

12

Strana od-do

"e202300573"

Kód UT WoS článku

001119805800001

EID výsledku v databázi Scopus

2-s2.0-85179354682