Oxidation and reduction of bis(imino)pyridine iron dicarbonyl complexes

Aaron M. Tondreau; Carsten Milsmann; Emil Lobkovsky; Paul J. Chirik

doi:10.1021/ic200730k

Oxidation and reduction of bis(imino)pyridine iron dicarbonyl complexes

Aaron M. Tondreau, Carsten Milsmann, Emil Lobkovsky, Paul J. Chirik

Chemistry

Research output: Contribution to journal › Review article › peer-review

59 Scopus citations

Abstract

The oxidation and reduction of a redox-active aryl-substituted bis(imino)pyridine iron dicarbonyl has been explored to determine whether electron-transfer events are ligand- or metal-based or a combination of both. A series of bis(imino)pyridine iron dicarbonyl compounds, [(^iPrPDI) Fe(CO)₂]^-, (^iPrPDI)Fe(CO)₂, and [(^iPrPDI)Fe(CO)₂]⁺ [^iPrPDI = 2,6-(2,6-ⁱPr₂C₆H₃N=CMe) ₂C₅H₃N], which differ by three oxidation states, were prepared and the electronic structures evaluated using a combination of spectroscopic techniques and, in two cases, [( ^iPrPDI)Fe(CO)₂]⁺ and [(^iPrPDI)Fe(CO) ₂], metrical parameters from X-ray diffraction. The data establish that the cationic iron dicarbonyl complex is best described as a low-spin iron(I) compound (S_Fe = ¹/₂) with a neutral bis(imino)pyridine chelate. The anionic iron dicarbonyl, [(^iPrPDI) Fe(CO)₂]^-, is also best described as an iron(I) compound but with a two-electron-reduced bis(imino)pyridine. The covalency of the neutral compound, (^iPrPDI)Fe(CO)₂, suggests that both the oxidative and reductive events are not ligand- or metal-localized but a result of the cooperativity of both entities.

Original language	English (US)
Pages (from-to)	9888-9895
Number of pages	8
Journal	Inorganic Chemistry
Volume	50
Issue number	20
DOIs	https://doi.org/10.1021/ic200730k
State	Published - Oct 17 2011

All Science Journal Classification (ASJC) codes

Inorganic Chemistry
Physical and Theoretical Chemistry

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10.1021/ic200730k

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title = "Oxidation and reduction of bis(imino)pyridine iron dicarbonyl complexes",

abstract = "The oxidation and reduction of a redox-active aryl-substituted bis(imino)pyridine iron dicarbonyl has been explored to determine whether electron-transfer events are ligand- or metal-based or a combination of both. A series of bis(imino)pyridine iron dicarbonyl compounds, [(iPrPDI) Fe(CO)2]-, (iPrPDI)Fe(CO)2, and [(iPrPDI)Fe(CO)2]+ [iPrPDI = 2,6-(2,6-iPr2C6H3N=CMe) 2C5H3N], which differ by three oxidation states, were prepared and the electronic structures evaluated using a combination of spectroscopic techniques and, in two cases, [( iPrPDI)Fe(CO)2]+ and [(iPrPDI)Fe(CO) 2], metrical parameters from X-ray diffraction. The data establish that the cationic iron dicarbonyl complex is best described as a low-spin iron(I) compound (SFe = 1/2) with a neutral bis(imino)pyridine chelate. The anionic iron dicarbonyl, [(iPrPDI) Fe(CO)2]-, is also best described as an iron(I) compound but with a two-electron-reduced bis(imino)pyridine. The covalency of the neutral compound, (iPrPDI)Fe(CO)2, suggests that both the oxidative and reductive events are not ligand- or metal-localized but a result of the cooperativity of both entities.",

author = "Tondreau, {Aaron M.} and Carsten Milsmann and Emil Lobkovsky and Chirik, {Paul J.}",

year = "2011",

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doi = "10.1021/ic200730k",

language = "English (US)",

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TY - JOUR

T1 - Oxidation and reduction of bis(imino)pyridine iron dicarbonyl complexes

AU - Tondreau, Aaron M.

AU - Milsmann, Carsten

AU - Lobkovsky, Emil

AU - Chirik, Paul J.

PY - 2011/10/17

Y1 - 2011/10/17

N2 - The oxidation and reduction of a redox-active aryl-substituted bis(imino)pyridine iron dicarbonyl has been explored to determine whether electron-transfer events are ligand- or metal-based or a combination of both. A series of bis(imino)pyridine iron dicarbonyl compounds, [(iPrPDI) Fe(CO)2]-, (iPrPDI)Fe(CO)2, and [(iPrPDI)Fe(CO)2]+ [iPrPDI = 2,6-(2,6-iPr2C6H3N=CMe) 2C5H3N], which differ by three oxidation states, were prepared and the electronic structures evaluated using a combination of spectroscopic techniques and, in two cases, [( iPrPDI)Fe(CO)2]+ and [(iPrPDI)Fe(CO) 2], metrical parameters from X-ray diffraction. The data establish that the cationic iron dicarbonyl complex is best described as a low-spin iron(I) compound (SFe = 1/2) with a neutral bis(imino)pyridine chelate. The anionic iron dicarbonyl, [(iPrPDI) Fe(CO)2]-, is also best described as an iron(I) compound but with a two-electron-reduced bis(imino)pyridine. The covalency of the neutral compound, (iPrPDI)Fe(CO)2, suggests that both the oxidative and reductive events are not ligand- or metal-localized but a result of the cooperativity of both entities.

AB - The oxidation and reduction of a redox-active aryl-substituted bis(imino)pyridine iron dicarbonyl has been explored to determine whether electron-transfer events are ligand- or metal-based or a combination of both. A series of bis(imino)pyridine iron dicarbonyl compounds, [(iPrPDI) Fe(CO)2]-, (iPrPDI)Fe(CO)2, and [(iPrPDI)Fe(CO)2]+ [iPrPDI = 2,6-(2,6-iPr2C6H3N=CMe) 2C5H3N], which differ by three oxidation states, were prepared and the electronic structures evaluated using a combination of spectroscopic techniques and, in two cases, [( iPrPDI)Fe(CO)2]+ and [(iPrPDI)Fe(CO) 2], metrical parameters from X-ray diffraction. The data establish that the cationic iron dicarbonyl complex is best described as a low-spin iron(I) compound (SFe = 1/2) with a neutral bis(imino)pyridine chelate. The anionic iron dicarbonyl, [(iPrPDI) Fe(CO)2]-, is also best described as an iron(I) compound but with a two-electron-reduced bis(imino)pyridine. The covalency of the neutral compound, (iPrPDI)Fe(CO)2, suggests that both the oxidative and reductive events are not ligand- or metal-localized but a result of the cooperativity of both entities.

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JO - Inorganic Chemistry

JF - Inorganic Chemistry

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ER -

Oxidation and reduction of bis(imino)pyridine iron dicarbonyl complexes

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