Modulation of in:out and out:out conformations in [X.X′.X′′] phosphatranes by Lewis acids

Goar Sánchez-Sanz; Cristina Trujillo; Ibon Alkorta; José Elguero

doi:10.1039/c7cp03661b

Modulation of in:out and out:out conformations in [X.X′.X′′] phosphatranes by Lewis acids

Goar Sánchez-Sanz^*, Cristina Trujillo, Ibon Alkorta, José Elguero

^*Corresponding author for this work

CSIC - Instituto de Química Médica

Research output: Contribution to journal › Article › peer-review

Abstract

A theoretical study of [X.X′.X′′]phosphatrane:Lewis acid complexes has been carried out in order to analyze how the in:out and out:out conformations can be modulated by the interaction with Lewis acids (LA). It has been found that in:out structures are more stable in larger systems i.e. in [4.4.3]:LA and [4.4.4]:LA than in [3.3.3]:LA and [4.3.3]:LA. The results obtained for the relative energies in conjunction with electron density properties showed that upon complexation, in:out conformers become more stable with the increasing acidity of the corresponding Lewis acid. In fact, the binding energies found for in:out complexes are larger than those obtained for out:out complexes. The complexes with the largest relative energy favoring the in:out structure correspond to those with charged Lewis acids, followed by the complexes with ClF. In all cases, the complexes are cooperative, reaching a maximum value of 168.5 kJ mol^-1 for the [4.3.3]:F⁺ complex.

Original language	English
Pages (from-to)	20647-20656
Number of pages	10
Journal	Physical Chemistry Chemical Physics
Volume	19
Issue number	31
DOIs	https://doi.org/10.1039/c7cp03661b
Publication status	Published - 21 Aug 2017

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title = "Modulation of in:out and out:out conformations in [X.X′.X′′] phosphatranes by Lewis acids",

abstract = "A theoretical study of [X.X′.X′′]phosphatrane:Lewis acid complexes has been carried out in order to analyze how the in:out and out:out conformations can be modulated by the interaction with Lewis acids (LA). It has been found that in:out structures are more stable in larger systems i.e. in [4.4.3]:LA and [4.4.4]:LA than in [3.3.3]:LA and [4.3.3]:LA. The results obtained for the relative energies in conjunction with electron density properties showed that upon complexation, in:out conformers become more stable with the increasing acidity of the corresponding Lewis acid. In fact, the binding energies found for in:out complexes are larger than those obtained for out:out complexes. The complexes with the largest relative energy favoring the in:out structure correspond to those with charged Lewis acids, followed by the complexes with ClF. In all cases, the complexes are cooperative, reaching a maximum value of 168.5 kJ mol-1 for the [4.3.3]:F+ complex.",

author = "Goar S{\'a}nchez-Sanz and Cristina Trujillo and Ibon Alkorta and Jos{\'e} Elguero",

note = "Publisher Copyright: {\textcopyright} 2017 the Owner Societies.",

year = "2017",

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doi = "10.1039/c7cp03661b",

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T1 - Modulation of in:out and out:out conformations in [X.X′.X′′] phosphatranes by Lewis acids

AU - Sánchez-Sanz, Goar

AU - Trujillo, Cristina

AU - Alkorta, Ibon

AU - Elguero, José

PY - 2017/8/21

Y1 - 2017/8/21

N2 - A theoretical study of [X.X′.X′′]phosphatrane:Lewis acid complexes has been carried out in order to analyze how the in:out and out:out conformations can be modulated by the interaction with Lewis acids (LA). It has been found that in:out structures are more stable in larger systems i.e. in [4.4.3]:LA and [4.4.4]:LA than in [3.3.3]:LA and [4.3.3]:LA. The results obtained for the relative energies in conjunction with electron density properties showed that upon complexation, in:out conformers become more stable with the increasing acidity of the corresponding Lewis acid. In fact, the binding energies found for in:out complexes are larger than those obtained for out:out complexes. The complexes with the largest relative energy favoring the in:out structure correspond to those with charged Lewis acids, followed by the complexes with ClF. In all cases, the complexes are cooperative, reaching a maximum value of 168.5 kJ mol-1 for the [4.3.3]:F+ complex.

AB - A theoretical study of [X.X′.X′′]phosphatrane:Lewis acid complexes has been carried out in order to analyze how the in:out and out:out conformations can be modulated by the interaction with Lewis acids (LA). It has been found that in:out structures are more stable in larger systems i.e. in [4.4.3]:LA and [4.4.4]:LA than in [3.3.3]:LA and [4.3.3]:LA. The results obtained for the relative energies in conjunction with electron density properties showed that upon complexation, in:out conformers become more stable with the increasing acidity of the corresponding Lewis acid. In fact, the binding energies found for in:out complexes are larger than those obtained for out:out complexes. The complexes with the largest relative energy favoring the in:out structure correspond to those with charged Lewis acids, followed by the complexes with ClF. In all cases, the complexes are cooperative, reaching a maximum value of 168.5 kJ mol-1 for the [4.3.3]:F+ complex.

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JO - Physical Chemistry Chemical Physics

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IS - 31

ER -

Modulation of in:out and out:out conformations in [X.X′.X′′] phosphatranes by Lewis acids

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