Back to basics: identification of reaction intermediates in the mechanism of a classic ligand substitution reaction on Vaska's complex

Durango-García, Clara J.; Jalife, Said; Cabellos, José Luis; Martínez, Saúl H.; Jiménez-Halla, J. Oscar C.; Pan, Sudip; Merino, Gabriel; Montiel‐Palma, Virginia

doi:10.1039/c5ra20969b

Cited by 4 publications

(3 citation statements)

References 61 publications

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“…[24] All the previousc omputations were done using the Gaussian09program. [29][30][31][32][33][34] The EDA decomposes the instantaneous interaction energy, DE int ,b etween the helicene and E + into four terms;aq uasi-classical electrostatic interaction DV elstat ,aDE Pauli caused by repulsion between same spin electrons, and an orbital interaction DE orb term as ar esult of the stabilizing orbital interaction. [28] We have used EDA to study as eries of organometallicc omplexes before.…”

Section: Computationaldetailsmentioning

confidence: 99%

“…[28] We have used EDA to study as eries of organometallicc omplexes before. [29][30][31][32][33][34] The EDA decomposes the instantaneous interaction energy, DE int ,b etween the helicene and E + into four terms;aq uasi-classical electrostatic interaction DV elstat ,aDE Pauli caused by repulsion between same spin electrons, and an orbital interaction DE orb term as ar esult of the stabilizing orbital interaction. Moreover,adispersion correction DE disp is also added to the DE int due to the employment of the PBE-D3 functional.…”

Section: Computationaldetailsmentioning

confidence: 99%

“…Additionally, the nature of the interactions was analyzed by the Energy Decomposition Analysis (EDA) at the PBE‐D3/TZ2P level using the previously optimized geometries via the ADF 2016 package . We have used EDA to study a series of organometallic complexes before . The EDA decomposes the instantaneous interaction energy, Δ E int , between the helicene and E + into four terms; a quasi‐classical electrostatic interaction Δ V elstat , a Δ E Pauli caused by repulsion between same spin electrons, and an orbital interaction Δ E orb term as a result of the stabilizing orbital interaction.…”

Section: Computational Detailsmentioning

confidence: 99%

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Bonding and Mobility of Alkali Metals in Helicenes

Barroso

Murillo

Martínez‐Guajardo

et al. 2018

Chemistry A European J

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In this work, we analyze the interactions of alkali metal cations with [6]- and [14]helicene and the cation mobility of therein. We found that the distortion of the carbon skeleton is the reason that some of the structures which are local minima for the smallest cations are not energetically stable for K , Rb , and Cs . Also, the most favorable complexes are those where the cation is interacting with two rings forming a metallocene-like structure, except for the largest cation Cs , where the distortion provoked by the size of the cation destabilizes the complex. As far as mobility is concerned, the smallest cations, particularly Na , are the ones that can move most efficiently. In [6]helicene, the mobility is limited by the capture of the cation forming the metallocene-like structure. In larger helicenes, the energy barriers for the cation to move are similar both inside and outside the helix. However, complexes with the cation between two layers are more energetically favored so that the movement will be preferred in that region. The bonding analysis reveals that interactions with no less than 50 % of orbital contribution are taking place for the series of E -[6]helicene. Particularly, the complexes of Li show remarkable orbital character (72.5-81.6 %).

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