π-Donor/acceptor effect on Lindqvist type polyoxomolibdates because of various multiple-bonded nitrogenous ligands

Desmond Mac Leod Carey; Alvaro Muñoz-Castro; Carlos J. Bustos; Juan M. Manríquez; Ramiro Arratia-Pérez

doi:10.1021/jp0727594

π-Donor/acceptor effect on Lindqvist type polyoxomolibdates because of various multiple-bonded nitrogenous ligands

Desmond Mac Leod Carey, Alvaro Muñoz-Castro, Carlos J. Bustos, Juan M. Manríquez, Ramiro Arratia-Pérez

Exact Sciences School

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

15 Citations (Scopus)

Abstract

The electronic structures of Lindqvist type functionalized polyoxometalates (POM) ([Mo₆O₁₈R]^n-- R = O, NO, NAr, NNAr, NNAr₂; n = 2, 3) have been investigated using density functional methods. We discuss the role of the replacement of terminal oxo ligands by π-donor/acceptor multiple-bonded nitrogenous ligands on the basis of geometrical parameters, charge analyses, reactivity indexes, and vibrational spectra. The calculated reactivity indexes (chemical potential, electronegativity, hardness, and electrophilicity) indicate that the most reactive functionalized POMs are those substituted by π-acceptor ligands. These π-acceptor ligands induce a decrease in the hardness and an increase in the chemical potential and electrophilicity, thus increasing the reactivity. Our calculations are in reasonable agreement with reported experimental data.

Original language	English
Pages (from-to)	6563-6567
Number of pages	5
Journal	Journal of Physical Chemistry A
Volume	111
Issue number	28
DOIs	https://doi.org/10.1021/jp0727594
Publication status	Published - 19 Jul 2007

ASJC Scopus subject areas

Physical and Theoretical Chemistry

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10.1021/jp0727594

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title = "π-Donor/acceptor effect on Lindqvist type polyoxomolibdates because of various multiple-bonded nitrogenous ligands",

abstract = "The electronic structures of Lindqvist type functionalized polyoxometalates (POM) ([Mo6O18R]n-- R = O, NO, NAr, NNAr, NNAr2; n = 2, 3) have been investigated using density functional methods. We discuss the role of the replacement of terminal oxo ligands by π-donor/acceptor multiple-bonded nitrogenous ligands on the basis of geometrical parameters, charge analyses, reactivity indexes, and vibrational spectra. The calculated reactivity indexes (chemical potential, electronegativity, hardness, and electrophilicity) indicate that the most reactive functionalized POMs are those substituted by π-acceptor ligands. These π-acceptor ligands induce a decrease in the hardness and an increase in the chemical potential and electrophilicity, thus increasing the reactivity. Our calculations are in reasonable agreement with reported experimental data.",

author = "Carey, {Desmond Mac Leod} and Alvaro Mu{\~n}oz-Castro and Bustos, {Carlos J.} and Manr{\'i}quez, {Juan M.} and Ramiro Arratia-P{\'e}rez",

year = "2007",

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doi = "10.1021/jp0727594",

language = "English",

volume = "111",

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journal = "Journal of Physical Chemistry A",

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T1 - π-Donor/acceptor effect on Lindqvist type polyoxomolibdates because of various multiple-bonded nitrogenous ligands

AU - Carey, Desmond Mac Leod

AU - Muñoz-Castro, Alvaro

AU - Bustos, Carlos J.

AU - Manríquez, Juan M.

AU - Arratia-Pérez, Ramiro

PY - 2007/7/19

Y1 - 2007/7/19

N2 - The electronic structures of Lindqvist type functionalized polyoxometalates (POM) ([Mo6O18R]n-- R = O, NO, NAr, NNAr, NNAr2; n = 2, 3) have been investigated using density functional methods. We discuss the role of the replacement of terminal oxo ligands by π-donor/acceptor multiple-bonded nitrogenous ligands on the basis of geometrical parameters, charge analyses, reactivity indexes, and vibrational spectra. The calculated reactivity indexes (chemical potential, electronegativity, hardness, and electrophilicity) indicate that the most reactive functionalized POMs are those substituted by π-acceptor ligands. These π-acceptor ligands induce a decrease in the hardness and an increase in the chemical potential and electrophilicity, thus increasing the reactivity. Our calculations are in reasonable agreement with reported experimental data.

AB - The electronic structures of Lindqvist type functionalized polyoxometalates (POM) ([Mo6O18R]n-- R = O, NO, NAr, NNAr, NNAr2; n = 2, 3) have been investigated using density functional methods. We discuss the role of the replacement of terminal oxo ligands by π-donor/acceptor multiple-bonded nitrogenous ligands on the basis of geometrical parameters, charge analyses, reactivity indexes, and vibrational spectra. The calculated reactivity indexes (chemical potential, electronegativity, hardness, and electrophilicity) indicate that the most reactive functionalized POMs are those substituted by π-acceptor ligands. These π-acceptor ligands induce a decrease in the hardness and an increase in the chemical potential and electrophilicity, thus increasing the reactivity. Our calculations are in reasonable agreement with reported experimental data.

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U2 - 10.1021/jp0727594

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SN - 1089-5639

VL - 111

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EP - 6567

JO - Journal of Physical Chemistry A

JF - Journal of Physical Chemistry A

IS - 28

ER -

π-Donor/acceptor effect on Lindqvist type polyoxomolibdates because of various multiple-bonded nitrogenous ligands

Abstract

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