Haptotropic rearrangements in heterocycles-ML(n) complexes. I. [Thiophene-Rh(PH3)3]+

Helena Diez Y Riega; Luis Rincón; Rafael Almeida

doi:10.1016/S0166-1280(99)00247-X

Haptotropic rearrangements in heterocycles-ML(n) complexes. I. [Thiophene-Rh(PH₃)₃]⁺

Helena Diez Y Riega, Luis Rincón, Rafael Almeida

Universidad de los Andes Mérida

Producción científica: Contribución a una revista › Artículo › revisión exhaustiva

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Resumen

A theoretical analysis of the haptotropic rearrangements involving thiophene and [Rh(PH₃)₃]⁺ is presented. This haptotropic rearrangement is involved in the C-S bond activation of thiophene by d⁸-ML₃ fragments. In this study, two theory levels, the second order Moller-Plesset perturbation theory (MP2) and density-functional theory (DFT-B3LYP), are employed. The pathway discussed in this paper connects an η⁴ coordination mode with an η³ one. The results suggest that for the fragment studied in this work, an η³ precursor of the C-S cleavage is preferred over the other one proposed in the literature.

Idioma original	Inglés
Páginas (desde-hasta)	259-266
Número de páginas	8
Publicación	Journal of Molecular Structure: THEOCHEM
Volumen	493
N.º	1-3
DOI	https://doi.org/10.1016/S0166-1280(99)00247-X
Estado	Publicada - 15 dic. 1999
Publicado de forma externa	Sí

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@article{971459ea6fd940209b226b2bf5e919cb,

title = "Haptotropic rearrangements in heterocycles-ML(n) complexes. I. [Thiophene-Rh(PH3)3]+",

abstract = "A theoretical analysis of the haptotropic rearrangements involving thiophene and [Rh(PH3)3]+ is presented. This haptotropic rearrangement is involved in the C-S bond activation of thiophene by d8-ML3 fragments. In this study, two theory levels, the second order Moller-Plesset perturbation theory (MP2) and density-functional theory (DFT-B3LYP), are employed. The pathway discussed in this paper connects an η4 coordination mode with an η3 one. The results suggest that for the fragment studied in this work, an η3 precursor of the C-S cleavage is preferred over the other one proposed in the literature.",

keywords = "Ab initio calculations, DFT calculations, Haptotropic rearrangements, Thiophene coordination",

author = "{Diez Y Riega}, Helena and Luis Rinc{\'o}n and Rafael Almeida",

note = "Funding Information: This research was supported by CONICIT through the Computational Catalysis Project (Grant 6970006167) and the Consejo de Desarrollo Cient{\'ı}fico, Human{\'ı}stico y Tecnol{\'o}gico of the Universidad de Los Andes (CDCHT-ULA, Grant C-729-95). We thank to CeCalCULA for its continued computational support. The authors are indebted to Dr R.A. Sanchez-Delgado for his interest and discussions.",

year = "1999",

month = dec,

day = "15",

doi = "10.1016/S0166-1280(99)00247-X",

language = "Ingl{\'e}s",

volume = "493",

pages = "259--266",

journal = "Journal of Molecular Structure: THEOCHEM",

issn = "0166-1280",

number = "1-3",

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TY - JOUR

T1 - Haptotropic rearrangements in heterocycles-ML(n) complexes. I. [Thiophene-Rh(PH3)3]+

AU - Diez Y Riega, Helena

AU - Rincón, Luis

AU - Almeida, Rafael

N1 - Funding Information: This research was supported by CONICIT through the Computational Catalysis Project (Grant 6970006167) and the Consejo de Desarrollo Cientı́fico, Humanı́stico y Tecnológico of the Universidad de Los Andes (CDCHT-ULA, Grant C-729-95). We thank to CeCalCULA for its continued computational support. The authors are indebted to Dr R.A. Sanchez-Delgado for his interest and discussions.

PY - 1999/12/15

Y1 - 1999/12/15

N2 - A theoretical analysis of the haptotropic rearrangements involving thiophene and [Rh(PH3)3]+ is presented. This haptotropic rearrangement is involved in the C-S bond activation of thiophene by d8-ML3 fragments. In this study, two theory levels, the second order Moller-Plesset perturbation theory (MP2) and density-functional theory (DFT-B3LYP), are employed. The pathway discussed in this paper connects an η4 coordination mode with an η3 one. The results suggest that for the fragment studied in this work, an η3 precursor of the C-S cleavage is preferred over the other one proposed in the literature.

AB - A theoretical analysis of the haptotropic rearrangements involving thiophene and [Rh(PH3)3]+ is presented. This haptotropic rearrangement is involved in the C-S bond activation of thiophene by d8-ML3 fragments. In this study, two theory levels, the second order Moller-Plesset perturbation theory (MP2) and density-functional theory (DFT-B3LYP), are employed. The pathway discussed in this paper connects an η4 coordination mode with an η3 one. The results suggest that for the fragment studied in this work, an η3 precursor of the C-S cleavage is preferred over the other one proposed in the literature.

KW - Ab initio calculations

KW - DFT calculations

KW - Haptotropic rearrangements

KW - Thiophene coordination

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U2 - 10.1016/S0166-1280(99)00247-X

DO - 10.1016/S0166-1280(99)00247-X

M3 - Artículo

AN - SCOPUS:0033572401

SN - 0166-1280

VL - 493

SP - 259

EP - 266

JO - Journal of Molecular Structure: THEOCHEM

JF - Journal of Molecular Structure: THEOCHEM

IS - 1-3