Mechanical vs Electronic Strain: Calculated Configurations of Alkynyl-Pt(II)-Phosphine Macrocycles

Kód výsledku v IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F61388963%3A_____%2F20%3A00524023" target="_blank" >RIV/61388963:_____/20:00524023 - isvavai.cz</a>

Výsledek na webu

<a href="https://pubs.acs.org/doi/10.1021/acs.organomet.9b00872" target="_blank" >https://pubs.acs.org/doi/10.1021/acs.organomet.9b00872</a>

DOI - Digital Object Identifier

<a href="http://dx.doi.org/10.1021/acs.organomet.9b00872" target="_blank" >10.1021/acs.organomet.9b00872</a>

Jazyk výsledku

angličtina

Název v původním jazyce

Mechanical vs Electronic Strain: Calculated Configurations of Alkynyl-Pt(II)-Phosphine Macrocycles

Popis výsledku v původním jazyce

Optimized geometries of macrocycles composed of four Pt(PR3)2 linkers and four rods terminated with ethynyl or pyridyl moieties have been calculated at the PBE0/Def2-TZVPP//PBE0/Def2-SVP level of density functional theory for all combinations of cis and trans configurations at the Pt centers. For uncharged complexes with four p,p′-bis(ethynyl)biphenyl rods and neutral Pt centers, the energy of the planar oval-shaped all-trans isomer lies 17 kcal/mol below that of the puckered square-shaped all-cis isomer. In this case, the electronic strain associated with the cis arrangement at the Pt atoms overrules the mechanical strain associated with the bending of triple bonds. For cationic complexes containing two bipyridyl and two p,p′-bis(ethynyl)biphenyl rods, with a +1 charge on each Pt center, a puckered rectangular structure with all-cis Pt centers is found to be 38 kcal/mol lower in energy than the isomer with all four Pt centers trans. The results have been analyzed in terms of three additive factors, referred to as electronic, mechanical, and electrostatic strains.

Název v anglickém jazyce

Mechanical vs Electronic Strain: Calculated Configurations of Alkynyl-Pt(II)-Phosphine Macrocycles

Popis výsledku anglicky

Optimized geometries of macrocycles composed of four Pt(PR3)2 linkers and four rods terminated with ethynyl or pyridyl moieties have been calculated at the PBE0/Def2-TZVPP//PBE0/Def2-SVP level of density functional theory for all combinations of cis and trans configurations at the Pt centers. For uncharged complexes with four p,p′-bis(ethynyl)biphenyl rods and neutral Pt centers, the energy of the planar oval-shaped all-trans isomer lies 17 kcal/mol below that of the puckered square-shaped all-cis isomer. In this case, the electronic strain associated with the cis arrangement at the Pt atoms overrules the mechanical strain associated with the bending of triple bonds. For cationic complexes containing two bipyridyl and two p,p′-bis(ethynyl)biphenyl rods, with a +1 charge on each Pt center, a puckered rectangular structure with all-cis Pt centers is found to be 38 kcal/mol lower in energy than the isomer with all four Pt centers trans. The results have been analyzed in terms of three additive factors, referred to as electronic, mechanical, and electrostatic strains.

Druh

J_imp - Článek v periodiku v databázi Web of Science

CEP obor

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OECD FORD obor

10401 - Organic chemistry

Projekt

—

Návaznosti

I - Institucionalni podpora na dlouhodoby koncepcni rozvoj vyzkumne organizace

Rok uplatnění

2020

Kód důvěrnosti údajů

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

Název periodika

Organometallics

ISSN

0276-7333

e-ISSN

—

Svazek periodika

39

Číslo periodika v rámci svazku

8

Stát vydavatele periodika

US - Spojené státy americké

Počet stran výsledku

7

Strana od-do

1195-1201

Kód UT WoS článku

000529146900008

EID výsledku v databázi Scopus

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