New Insight into the Nature of Bonding in the Dimers of Lappert's Stannylene and Its Ge Analogs: A Quantum Mechanical Study

Result code in IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F61388963%3A_____%2F16%3A00459398" target="_blank" >RIV/61388963:_____/16:00459398 - isvavai.cz</a>

Alternative codes found

RIV/61989592:15310/16:33161582 RIV/00216275:25310/16:39901642

Result on the web

<a href="http://dx.doi.org/10.1021/acs.jctc.6b00065" target="_blank" >http://dx.doi.org/10.1021/acs.jctc.6b00065</a>

DOI - Digital Object Identifier

<a href="http://dx.doi.org/10.1021/acs.jctc.6b00065" target="_blank" >10.1021/acs.jctc.6b00065</a>

Result language

angličtina

Original language name

New Insight into the Nature of Bonding in the Dimers of Lappert's Stannylene and Its Ge Analogs: A Quantum Mechanical Study

Original language description

The strength and nature of the connection in Lappert's stannylene dimer ({Sn[CH(SiMe3)(2)](2)}(2)) and its smaller analogs, simplified stannylenes, as well as similar Ge complexes were studied by means of DFT-D3 calculations, energy decomposition analysis (EDA), electrostatic potential (ESP), and natural population analysis. The trans-bent structure of the investigated molecules was rationalized by means of EDA, ESP, and molecular orbital (MO) analyses. The different ESPs for the monomers studied are a result of different hybridization of the Sn (Ge) atoms. The comparably strong stabilization in the largest and the smallest systems with a dramatically different substituent size is explained by the different nature of the binding between monomers. For all complexes, it has been found that the total attractive interaction is mostly provided by the electrostatic component (>50%), followed by orbital interaction and dispersion. In the largest molecule (Lappert's stannylene), the dispersion interaction plays a more significant role in stabilization and its magnitude is comparable to that of orbital interaction; on the other hand in the smallest molecule (SnH2), where bulky substituents are replaced by H only, the dispersion energy is less important and the E-E bond is more of a charge transfer character, caused by donor-acceptor orbital interactions. The charge transfer in Ge dimers is greater than in the Sn ones due to shorter distances between monomers, which cause better (HOMO/LUMO) overlaps. The easier dimerization of Lappert's stannylene as compared to Kira's ({Sn[(Me3Si)(2)CHCH2CH2CH(SiMe3)(2)-x(2)C,C']}) stannylene is explained by the different orientation of their substituents-asymmetry promotes dimerization.

Czech name

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Czech description

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Type

J_x - Unclassified - Peer-reviewed scientific article (Jimp, Jsc and Jost)

CEP classification

CF - Physical chemistry and theoretical chemistry

OECD FORD branch

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Project

Result was created during the realization of more than one project. More information in the Projects tab.

Continuities

I - Institucionalni podpora na dlouhodoby koncepcni rozvoj vyzkumne organizace

Publication year

2016

Confidentiality

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

Name of the periodical

Journal of Chemical Theory and Computation

ISSN

1549-9618

e-ISSN

—

Volume of the periodical

12

Issue of the periodical within the volume

4

Country of publishing house

US - UNITED STATES

Number of pages

9

Pages from-to

1696-1704

UT code for WoS article

000374196400027

EID of the result in the Scopus database

2-s2.0-84964529955