Structural Evidence Concerning the Frontier Orbitals in [Fe2E2(CO)6]-2 (E = S, Se): Redox-Active Dichalcogen Ligands

Timothy D. Weatherill; Thomas B. Rauchfuss; Robert A. Scott

doi:10.1021/ic00229a033

Structural Evidence Concerning the Frontier Orbitals in [Fe₂E₂(CO)₆]^-2 (E = S, Se): Redox-Active Dichalcogen Ligands

Timothy D. Weatherill, Thomas B. Rauchfuss, Robert A. Scott

Chemistry

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Abstract

Fe and Se extended X-ray absorption fine structure (EXAFS) data have been used to determine the structures of the Fe₂E₂ (E = S, Se) cores of the following compounds: [Fe₂E₂(CO)₆]^z (z = 0, 2-), Fe₂(μ-ER)₂(CO)₆ (R = alkyl), [Fe₂E₂(NO)₄]^2-, and Fe₂(μ-ER)₂(NO)₄. For the carbonyl compounds, the Fe EXAFS results indicate that the Fe-C, Fe-Fe, and Fe-E distances change little upon conversion of Fe₂(E₂)(CO)₆ to [Fe₂E₂(CO)₆]^2- and Fe₂(μ-ER)₂(CO)₆. The Se EXAFS results are consistent with the Fe EXAFS data, also showing that the two-electron reduction of Fe₂(Se₂)(CO)₆ results in breaking of the Se-Se bond. The Fe and Se EXAFS of the related nitrosyls [Fe₂E₂(NO)₄]^2- and Fe₂(μ-ER)₂(NO)₄ confirm that the Fe₂E₂ cores of these complexes are similar. All of the EXAFS results are consistent with the LUMO of Fe₂(E₂)(CO)₆, being mainly E-E antibonding in character.

Original language	English (US)
Pages (from-to)	1466-1472
Number of pages	7
Journal	Inorganic Chemistry
Volume	25
Issue number	9
DOIs	https://doi.org/10.1021/ic00229a033
State	Published - 1986

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Physical and Theoretical Chemistry
Inorganic Chemistry

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@article{272874d84b454af485bb178266f649aa,

title = "Structural Evidence Concerning the Frontier Orbitals in [Fe2E2(CO)6]-2 (E = S, Se): Redox-Active Dichalcogen Ligands",

abstract = "Fe and Se extended X-ray absorption fine structure (EXAFS) data have been used to determine the structures of the Fe2E2 (E = S, Se) cores of the following compounds: [Fe2E2(CO)6]z (z = 0, 2-), Fe2(μ-ER)2(CO)6 (R = alkyl), [Fe2E2(NO)4]2-, and Fe2(μ-ER)2(NO)4. For the carbonyl compounds, the Fe EXAFS results indicate that the Fe-C, Fe-Fe, and Fe-E distances change little upon conversion of Fe2(E2)(CO)6 to [Fe2E2(CO)6]2- and Fe2(μ-ER)2(CO)6. The Se EXAFS results are consistent with the Fe EXAFS data, also showing that the two-electron reduction of Fe2(Se2)(CO)6 results in breaking of the Se-Se bond. The Fe and Se EXAFS of the related nitrosyls [Fe2E2(NO)4]2- and Fe2(μ-ER)2(NO)4 confirm that the Fe2E2 cores of these complexes are similar. All of the EXAFS results are consistent with the LUMO of Fe2(E2)(CO)6, being mainly E-E antibonding in character.",

author = "Weatherill, {Timothy D.} and Rauchfuss, {Thomas B.} and Scott, {Robert A.}",

year = "1986",

doi = "10.1021/ic00229a033",

language = "English (US)",

volume = "25",

pages = "1466--1472",

journal = "Inorganic Chemistry",

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publisher = "American Chemical Society",

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TY - JOUR

T1 - Structural Evidence Concerning the Frontier Orbitals in [Fe2E2(CO)6]-2 (E = S, Se)

T2 - Redox-Active Dichalcogen Ligands

AU - Weatherill, Timothy D.

AU - Rauchfuss, Thomas B.

AU - Scott, Robert A.

PY - 1986

Y1 - 1986

N2 - Fe and Se extended X-ray absorption fine structure (EXAFS) data have been used to determine the structures of the Fe2E2 (E = S, Se) cores of the following compounds: [Fe2E2(CO)6]z (z = 0, 2-), Fe2(μ-ER)2(CO)6 (R = alkyl), [Fe2E2(NO)4]2-, and Fe2(μ-ER)2(NO)4. For the carbonyl compounds, the Fe EXAFS results indicate that the Fe-C, Fe-Fe, and Fe-E distances change little upon conversion of Fe2(E2)(CO)6 to [Fe2E2(CO)6]2- and Fe2(μ-ER)2(CO)6. The Se EXAFS results are consistent with the Fe EXAFS data, also showing that the two-electron reduction of Fe2(Se2)(CO)6 results in breaking of the Se-Se bond. The Fe and Se EXAFS of the related nitrosyls [Fe2E2(NO)4]2- and Fe2(μ-ER)2(NO)4 confirm that the Fe2E2 cores of these complexes are similar. All of the EXAFS results are consistent with the LUMO of Fe2(E2)(CO)6, being mainly E-E antibonding in character.

AB - Fe and Se extended X-ray absorption fine structure (EXAFS) data have been used to determine the structures of the Fe2E2 (E = S, Se) cores of the following compounds: [Fe2E2(CO)6]z (z = 0, 2-), Fe2(μ-ER)2(CO)6 (R = alkyl), [Fe2E2(NO)4]2-, and Fe2(μ-ER)2(NO)4. For the carbonyl compounds, the Fe EXAFS results indicate that the Fe-C, Fe-Fe, and Fe-E distances change little upon conversion of Fe2(E2)(CO)6 to [Fe2E2(CO)6]2- and Fe2(μ-ER)2(CO)6. The Se EXAFS results are consistent with the Fe EXAFS data, also showing that the two-electron reduction of Fe2(Se2)(CO)6 results in breaking of the Se-Se bond. The Fe and Se EXAFS of the related nitrosyls [Fe2E2(NO)4]2- and Fe2(μ-ER)2(NO)4 confirm that the Fe2E2 cores of these complexes are similar. All of the EXAFS results are consistent with the LUMO of Fe2(E2)(CO)6, being mainly E-E antibonding in character.

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