DFT study on the electronic structure, energetics and spectral properties of several bis(organohydrazido(2-)) molybdenum complexes containing substituted phosphines and chloro atoms as ancillary ligands

Ximena Zárate, Eduardo Schott, Desmond Mac-Leod Carey, Carlos Bustos, Ramiro Arratia-Pérez

Resultado de la investigación: Article

4 Citas (Scopus)

Resumen

A theoretical study of the geometrical and electronic structure of several structurally related bis(organohydrazido(2-))-molybdenum complexes containing substituted phosphines and chloro atoms as ancillary ligands, of formula [Mo(NNPh2)2Cl2(PPh3)2] (1), [Mo(NNPh2)2Cl2(PMePh2)2] (2), [Mo(NNPh2)2Cl2(PMe2Ph)2] (3), [Mo(NNPh2)2Cl2(PMe3)2] (4) and [Mo(NNPh2)2Cl2(PH3)2] (5), was carried out. In order to analyze the electronic effects when the phosphines are changed, a decomposition energy analysis was performed, finding that the Mo-Cl interactions have long distance and ionic character with poor " p" antibonding contributions. Besides, the metal-phosphine interactions have little covalent character, while the Mo-hydrazido(-2) interaction with significant orbital contribution, indicates a strong covalent character with respect to the rest of the ligands. On the other hand, the calculated electronic transitions using the Time-Dependent Density Functional Theory (TDDFT) are also presented at GGA and B3LYP theoretical levels, and despite of the limitations of the first method, we obtained a good correlation with B3LYP analysis performed. Also, the calculated excitations are in good agreement with the experimental data for (2) and (3), moreover, we were able to predict the electronic transitions that could be observed in the proposed (1), (4) and (5) complexes and these results indicate that these compounds are stable and they should be able to be synthesized.

Idioma originalEnglish
Páginas (desde-hasta)126-132
Número de páginas7
PublicaciónJournal of Molecular Structure: THEOCHEM
Volumen957
N.º1-3
DOI
EstadoPublished - 1 oct 2010

Huella dactilar

Phosphines
phosphine
Molybdenum
phosphines
Discrete Fourier transforms
Electronic structure
molybdenum
electronic structure
Ligands
Atoms
ligands
electronics
Density functional theory
atoms
Theoretical Models
Metals
interactions
Decomposition
density functional theory
decomposition

ASJC Scopus subject areas

  • Biochemistry
  • Condensed Matter Physics
  • Physical and Theoretical Chemistry

Citar esto

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title = "DFT study on the electronic structure, energetics and spectral properties of several bis(organohydrazido(2-)) molybdenum complexes containing substituted phosphines and chloro atoms as ancillary ligands",
abstract = "A theoretical study of the geometrical and electronic structure of several structurally related bis(organohydrazido(2-))-molybdenum complexes containing substituted phosphines and chloro atoms as ancillary ligands, of formula [Mo(NNPh2)2Cl2(PPh3)2] (1), [Mo(NNPh2)2Cl2(PMePh2)2] (2), [Mo(NNPh2)2Cl2(PMe2Ph)2] (3), [Mo(NNPh2)2Cl2(PMe3)2] (4) and [Mo(NNPh2)2Cl2(PH3)2] (5), was carried out. In order to analyze the electronic effects when the phosphines are changed, a decomposition energy analysis was performed, finding that the Mo-Cl interactions have long distance and ionic character with poor {"} p{"} antibonding contributions. Besides, the metal-phosphine interactions have little covalent character, while the Mo-hydrazido(-2) interaction with significant orbital contribution, indicates a strong covalent character with respect to the rest of the ligands. On the other hand, the calculated electronic transitions using the Time-Dependent Density Functional Theory (TDDFT) are also presented at GGA and B3LYP theoretical levels, and despite of the limitations of the first method, we obtained a good correlation with B3LYP analysis performed. Also, the calculated excitations are in good agreement with the experimental data for (2) and (3), moreover, we were able to predict the electronic transitions that could be observed in the proposed (1), (4) and (5) complexes and these results indicate that these compounds are stable and they should be able to be synthesized.",
keywords = "B3LYP, Bis(organohydrazido(2-)) molybdenum complexes, GGA, Molybdenum complexes, TDDFT",
author = "Ximena Z{\'a}rate and Eduardo Schott and {Mac-Leod Carey}, Desmond and Carlos Bustos and Ramiro Arratia-P{\'e}rez",
year = "2010",
month = "10",
day = "1",
doi = "10.1016/j.theochem.2010.07.021",
language = "English",
volume = "957",
pages = "126--132",
journal = "Computational and Theoretical Chemistry",
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TY - JOUR

T1 - DFT study on the electronic structure, energetics and spectral properties of several bis(organohydrazido(2-)) molybdenum complexes containing substituted phosphines and chloro atoms as ancillary ligands

AU - Zárate, Ximena

AU - Schott, Eduardo

AU - Mac-Leod Carey, Desmond

AU - Bustos, Carlos

AU - Arratia-Pérez, Ramiro

PY - 2010/10/1

Y1 - 2010/10/1

N2 - A theoretical study of the geometrical and electronic structure of several structurally related bis(organohydrazido(2-))-molybdenum complexes containing substituted phosphines and chloro atoms as ancillary ligands, of formula [Mo(NNPh2)2Cl2(PPh3)2] (1), [Mo(NNPh2)2Cl2(PMePh2)2] (2), [Mo(NNPh2)2Cl2(PMe2Ph)2] (3), [Mo(NNPh2)2Cl2(PMe3)2] (4) and [Mo(NNPh2)2Cl2(PH3)2] (5), was carried out. In order to analyze the electronic effects when the phosphines are changed, a decomposition energy analysis was performed, finding that the Mo-Cl interactions have long distance and ionic character with poor " p" antibonding contributions. Besides, the metal-phosphine interactions have little covalent character, while the Mo-hydrazido(-2) interaction with significant orbital contribution, indicates a strong covalent character with respect to the rest of the ligands. On the other hand, the calculated electronic transitions using the Time-Dependent Density Functional Theory (TDDFT) are also presented at GGA and B3LYP theoretical levels, and despite of the limitations of the first method, we obtained a good correlation with B3LYP analysis performed. Also, the calculated excitations are in good agreement with the experimental data for (2) and (3), moreover, we were able to predict the electronic transitions that could be observed in the proposed (1), (4) and (5) complexes and these results indicate that these compounds are stable and they should be able to be synthesized.

AB - A theoretical study of the geometrical and electronic structure of several structurally related bis(organohydrazido(2-))-molybdenum complexes containing substituted phosphines and chloro atoms as ancillary ligands, of formula [Mo(NNPh2)2Cl2(PPh3)2] (1), [Mo(NNPh2)2Cl2(PMePh2)2] (2), [Mo(NNPh2)2Cl2(PMe2Ph)2] (3), [Mo(NNPh2)2Cl2(PMe3)2] (4) and [Mo(NNPh2)2Cl2(PH3)2] (5), was carried out. In order to analyze the electronic effects when the phosphines are changed, a decomposition energy analysis was performed, finding that the Mo-Cl interactions have long distance and ionic character with poor " p" antibonding contributions. Besides, the metal-phosphine interactions have little covalent character, while the Mo-hydrazido(-2) interaction with significant orbital contribution, indicates a strong covalent character with respect to the rest of the ligands. On the other hand, the calculated electronic transitions using the Time-Dependent Density Functional Theory (TDDFT) are also presented at GGA and B3LYP theoretical levels, and despite of the limitations of the first method, we obtained a good correlation with B3LYP analysis performed. Also, the calculated excitations are in good agreement with the experimental data for (2) and (3), moreover, we were able to predict the electronic transitions that could be observed in the proposed (1), (4) and (5) complexes and these results indicate that these compounds are stable and they should be able to be synthesized.

KW - B3LYP

KW - Bis(organohydrazido(2-)) molybdenum complexes

KW - GGA

KW - Molybdenum complexes

KW - TDDFT

UR - http://www.scopus.com/inward/record.url?scp=77956189501&partnerID=8YFLogxK

U2 - 10.1016/j.theochem.2010.07.021

DO - 10.1016/j.theochem.2010.07.021

M3 - Article

AN - SCOPUS:77956189501

VL - 957

SP - 126

EP - 132

JO - Computational and Theoretical Chemistry

JF - Computational and Theoretical Chemistry

SN - 2210-271X

IS - 1-3

ER -