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

Result code in 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>

Result on the web

<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>

Result language

angličtina

Original language name

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

Original language description

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.

Czech name

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Czech description

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Type

J_imp - Article in a specialist periodical, which is included in the Web of Science database

CEP classification

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OECD FORD branch

10401 - Organic chemistry

Project

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Continuities

I - Institucionalni podpora na dlouhodoby koncepcni rozvoj vyzkumne organizace

Publication year

2020

Confidentiality

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

Name of the periodical

Organometallics

ISSN

0276-7333

e-ISSN

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Volume of the periodical

39

Issue of the periodical within the volume

8

Country of publishing house

US - UNITED STATES

Number of pages

7

Pages from-to

1195-1201

UT code for WoS article

000529146900008

EID of the result in the Scopus database

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