Nature and Strength of Metal-Chalcogen Multiple Bonds in High Oxidation State Complexes

Oscar González-Blanco; Vicenç Branchadell; Kereen Monteyne; Tom Ziegler

Nature and Strength of Metal-Chalcogen Multiple Bonds in High Oxidation State Complexes

Oscar González-Blanco, Vicenç Branchadell, Kereen Monteyne, Tom Ziegler

Department of Chemistry

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

23 Citations (Scopus)

Abstract

Density functional theory calculations have been carried out on the trigonal complexes OsO3E and MCl3E (M = V. Ta) and the square pyramidal systems MCl4E (M = Cr, Mo, W, Re) for E = O, S, Se, and Te as well as (C5H5)ReO3. All complexes were fully optimized, and the calculated geometrical parameters are in reasonable agreement with gas-phase electron diffraction data where available. The calculated M-E bond energies decrease from oxygen to tellurium, from bottom to top in a metal triad, and from left to right in a transition series. The trend setting factor is the donation from the dσ metal orbital to the pσ acceptor orbital on the chalcogen atom, The contribution from the chalcogen to metal π back-donation has a maximum for sulfur and selenium. However in relative terms, the contribution from the π back-donation to the total M-E bond energy increases from oxygen to tellurium. Comparisons are made to previous calculations and experimental data on M-E bond strengths.

Original language	English
Pages (from-to)	1744-1748
Journal	Inorganic Chemistry
Volume	37
Issue number	8
Publication status	Published - 1 Dec 1998

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title = "Nature and Strength of Metal-Chalcogen Multiple Bonds in High Oxidation State Complexes",

abstract = "Density functional theory calculations have been carried out on the trigonal complexes OsO3E and MCl3E (M = V. Ta) and the square pyramidal systems MCl4E (M = Cr, Mo, W, Re) for E = O, S, Se, and Te as well as (C5H5)ReO3. All complexes were fully optimized, and the calculated geometrical parameters are in reasonable agreement with gas-phase electron diffraction data where available. The calculated M-E bond energies decrease from oxygen to tellurium, from bottom to top in a metal triad, and from left to right in a transition series. The trend setting factor is the donation from the dσ metal orbital to the pσ acceptor orbital on the chalcogen atom, The contribution from the chalcogen to metal π back-donation has a maximum for sulfur and selenium. However in relative terms, the contribution from the π back-donation to the total M-E bond energy increases from oxygen to tellurium. Comparisons are made to previous calculations and experimental data on M-E bond strengths.",

author = "Oscar Gonz{\'a}lez-Blanco and Vicen{\c c} Branchadell and Kereen Monteyne and Tom Ziegler",

year = "1998",

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language = "English",

volume = "37",

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TY - JOUR

T1 - Nature and Strength of Metal-Chalcogen Multiple Bonds in High Oxidation State Complexes

AU - González-Blanco, Oscar

AU - Branchadell, Vicenç

AU - Monteyne, Kereen

AU - Ziegler, Tom

PY - 1998/12/1

Y1 - 1998/12/1

N2 - Density functional theory calculations have been carried out on the trigonal complexes OsO3E and MCl3E (M = V. Ta) and the square pyramidal systems MCl4E (M = Cr, Mo, W, Re) for E = O, S, Se, and Te as well as (C5H5)ReO3. All complexes were fully optimized, and the calculated geometrical parameters are in reasonable agreement with gas-phase electron diffraction data where available. The calculated M-E bond energies decrease from oxygen to tellurium, from bottom to top in a metal triad, and from left to right in a transition series. The trend setting factor is the donation from the dσ metal orbital to the pσ acceptor orbital on the chalcogen atom, The contribution from the chalcogen to metal π back-donation has a maximum for sulfur and selenium. However in relative terms, the contribution from the π back-donation to the total M-E bond energy increases from oxygen to tellurium. Comparisons are made to previous calculations and experimental data on M-E bond strengths.

AB - Density functional theory calculations have been carried out on the trigonal complexes OsO3E and MCl3E (M = V. Ta) and the square pyramidal systems MCl4E (M = Cr, Mo, W, Re) for E = O, S, Se, and Te as well as (C5H5)ReO3. All complexes were fully optimized, and the calculated geometrical parameters are in reasonable agreement with gas-phase electron diffraction data where available. The calculated M-E bond energies decrease from oxygen to tellurium, from bottom to top in a metal triad, and from left to right in a transition series. The trend setting factor is the donation from the dσ metal orbital to the pσ acceptor orbital on the chalcogen atom, The contribution from the chalcogen to metal π back-donation has a maximum for sulfur and selenium. However in relative terms, the contribution from the π back-donation to the total M-E bond energy increases from oxygen to tellurium. Comparisons are made to previous calculations and experimental data on M-E bond strengths.

M3 - Article

VL - 37

SP - 1744

EP - 1748

IS - 8

ER -