Roussin's Red Salt Revisited: Reactivity of Fe2(μ-E)2(NO)42− (E = S, Se, Te) and Related Compounds

Thomas B. Rauchfuss; Timothy D. Weatherill

doi:10.1021/ic00132a071

Roussin's Red Salt Revisited: Reactivity of Fe₂(μ-E)₂(NO)₄²⁻ (E = S, Se, Te) and Related Compounds

Thomas B. Rauchfuss, Timothy D. Weatherill

Chemistry

Research output: Contribution to journal › Comment/debate › peer-review

Abstract

In comparison with Fe₂(μ-S)₂(CO)₆^2-, Roussin's nitrosyl anion is considerably more stable and is reactive toward a narrower range of electrophiles. These observations are consistent with the view that nitric oxide is a more effective π-acid ligand than carbon monoxide. The net result is that the nucleophilicity of metal nitrosyl complexes is attenuated relative to the analogous carbonyls. An additional finding of this study relates to the synthetic utility of Fe₂(μ-I)₂(NO)₄. This diiron reagent allows one to prepare anhydrous solutions of Fe₂(μ-E)₂(NO)₄^2- (E = S, Se, Te). These intermediates permit the assembly of organochalcogenide ligands in situ, thus obviating the need for noxious and unstable ligand precursors.

Original language	English (US)
Pages (from-to)	827-830
Number of pages	4
Journal	Inorganic Chemistry
Volume	21
Issue number	2
DOIs	https://doi.org/10.1021/ic00132a071
State	Published - 1982

ASJC Scopus subject areas

Physical and Theoretical Chemistry
Inorganic Chemistry

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10.1021/ic00132a071

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@article{a828ae47b9e84c379d22005a2a4c7171,

title = "Roussin's Red Salt Revisited: Reactivity of Fe2(μ-E)2(NO)42− (E = S, Se, Te) and Related Compounds",

abstract = "In comparison with Fe2(μ-S)2(CO)62-, Roussin's nitrosyl anion is considerably more stable and is reactive toward a narrower range of electrophiles. These observations are consistent with the view that nitric oxide is a more effective π-acid ligand than carbon monoxide. The net result is that the nucleophilicity of metal nitrosyl complexes is attenuated relative to the analogous carbonyls. An additional finding of this study relates to the synthetic utility of Fe2(μ-I)2(NO)4. This diiron reagent allows one to prepare anhydrous solutions of Fe2(μ-E)2(NO)42- (E = S, Se, Te). These intermediates permit the assembly of organochalcogenide ligands in situ, thus obviating the need for noxious and unstable ligand precursors.",

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AU - Rauchfuss, Thomas B.

AU - Weatherill, Timothy D.

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N2 - In comparison with Fe2(μ-S)2(CO)62-, Roussin's nitrosyl anion is considerably more stable and is reactive toward a narrower range of electrophiles. These observations are consistent with the view that nitric oxide is a more effective π-acid ligand than carbon monoxide. The net result is that the nucleophilicity of metal nitrosyl complexes is attenuated relative to the analogous carbonyls. An additional finding of this study relates to the synthetic utility of Fe2(μ-I)2(NO)4. This diiron reagent allows one to prepare anhydrous solutions of Fe2(μ-E)2(NO)42- (E = S, Se, Te). These intermediates permit the assembly of organochalcogenide ligands in situ, thus obviating the need for noxious and unstable ligand precursors.

AB - In comparison with Fe2(μ-S)2(CO)62-, Roussin's nitrosyl anion is considerably more stable and is reactive toward a narrower range of electrophiles. These observations are consistent with the view that nitric oxide is a more effective π-acid ligand than carbon monoxide. The net result is that the nucleophilicity of metal nitrosyl complexes is attenuated relative to the analogous carbonyls. An additional finding of this study relates to the synthetic utility of Fe2(μ-I)2(NO)4. This diiron reagent allows one to prepare anhydrous solutions of Fe2(μ-E)2(NO)42- (E = S, Se, Te). These intermediates permit the assembly of organochalcogenide ligands in situ, thus obviating the need for noxious and unstable ligand precursors.

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