The reduction of [Fe(CO)2L2X2] = P(OMe)3, P(OiPr)3, PEt3; x= Br--from iron(II) to iron (0) via stable iron (I) intermediates

Helmut Kandler, Christine Gauss, Wolfgang Bidell, Stephan Rosenberger, Tobias Burgi, Igor L. Eremenko, Dario Veghini, Olli Orama, Peter Burger, Heinz Berke (Corresponding Author)

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Abstract

The reduction of [Fe(CO)2‐L2X2] (L = P(OMe)3 X = Br (1a), I (1b); L = P(OiPr)3, X = Br (2a), I (2b); L = PEt3, X = Br (3a), I (3b)) with Zn in dioxane (1a,b‐2a,b) or PhLi in ether (3a,b) led to formation of the corresponding dicarbonyl(halo)bis(phosphorus donor)iron(I) complexes (L = P(OMe)3, X = Br (4a), I (4b); L = P(OiPr)3, X = Br (5a), I (5b); L = PEt3, X = Br (6a), I (6b)). Slightly contaminated 5a,b and pure 6a,b were isolated as stable crystalline blue or blue‐green complexes. Complexes 4a,b were obtained, with only minor impurities, by comproportionation of 1a,b and the dicarbonyl(halo)bis‐(trimethylphosphite)ferrate anions 7a,b and characterized in THF solution.
The comproportionation products 5a,b‐6a,b were obtained in high yields by reaction of 2a,b‐3a,b with the dinitrogen complexes 13‐15. Further reduction of 4a,b‐6a,b or exhaustive reduction of 1a,b‐3a,b with sodium amalgam or iBuLi in THF afforded the nonisolable dicarbonyl‐(halo)bis(phosphorus donor)ferrate(o) anions (7a,b‐9a,b).
The latter were characterized by acidification with trifluoroacetic acid or acetic acid yielding stable dicarbonyl (halo) hydridobis (phosphorus donor)iron(II) complexes (L = P(OMe)3, X = Br (10a), I (10b); L = P(OiPr)3, X = Br (11a), I (11b);L = PEt3, X = Br (12a), I (12b)).
In the presence of N2, 8a was transformed into dinitrogen complex [Fe(CO)2{P(OiPr)3}2N2] (13). With 9a,b the reaction led to formation of [Fe‐(CO)2(PEt3)2)2N2] (14) and [{Fe(CO)2‐(PEt3)2}2(μ‐N2)] (15). In solution at low temperature (−90 to 0°C), the dinitrogen complexes 14 and 15 are in equilibrium with each other.
Complexes 13, 14, and 15 were characterized by IR, 1H, 13C, 31P, and 15N NMR spectroscopy. The structures of 5a, 6b, 14, and 15 were determined by X‐ray diffraction studies.

Original languageEnglish
Pages (from-to)541-548
JournalChemistry - A European Journal
Volume1
Issue number8
DOIs
Publication statusPublished - 1995
MoE publication typeA1 Journal article-refereed

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Carbon Monoxide
Phosphorus
Iron
Negative ions
Trifluoroacetic acid
Anions
Mercury amalgams
Acidification
Acetic acid
Trifluoroacetic Acid
Nuclear magnetic resonance spectroscopy
Ethers
Diffraction
Sodium
Acetic Acid
Ether
Impurities
Crystalline materials
Temperature
ferrate ion

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Kandler, Helmut ; Gauss, Christine ; Bidell, Wolfgang ; Rosenberger, Stephan ; Burgi, Tobias ; Eremenko, Igor L. ; Veghini, Dario ; Orama, Olli ; Burger, Peter ; Berke, Heinz. / The reduction of [Fe(CO)2L2X2] = P(OMe)3, P(OiPr)3, PEt3; x= Br--from iron(II) to iron (0) via stable iron (I) intermediates. In: Chemistry - A European Journal. 1995 ; Vol. 1, No. 8. pp. 541-548.
@article{6fc57dee10d1435e8d26944c4cc4b93b,
title = "The reduction of [Fe(CO)2L2X2] = P(OMe)3, P(OiPr)3, PEt3; x= Br--from iron(II) to iron (0) via stable iron (I) intermediates",
abstract = "The reduction of [Fe(CO)2‐L2X2] (L = P(OMe)3 X = Br (1a), I (1b); L = P(OiPr)3, X = Br (2a), I (2b); L = PEt3, X = Br (3a), I (3b)) with Zn in dioxane (1a,b‐2a,b) or PhLi in ether (3a,b) led to formation of the corresponding dicarbonyl(halo)bis(phosphorus donor)iron(I) complexes (L = P(OMe)3, X = Br (4a), I (4b); L = P(OiPr)3, X = Br (5a), I (5b); L = PEt3, X = Br (6a), I (6b)). Slightly contaminated 5a,b and pure 6a,b were isolated as stable crystalline blue or blue‐green complexes. Complexes 4a,b were obtained, with only minor impurities, by comproportionation of 1a,b and the dicarbonyl(halo)bis‐(trimethylphosphite)ferrate anions 7a,b and characterized in THF solution. The comproportionation products 5a,b‐6a,b were obtained in high yields by reaction of 2a,b‐3a,b with the dinitrogen complexes 13‐15. Further reduction of 4a,b‐6a,b or exhaustive reduction of 1a,b‐3a,b with sodium amalgam or iBuLi in THF afforded the nonisolable dicarbonyl‐(halo)bis(phosphorus donor)ferrate(o) anions (7a,b‐9a,b). The latter were characterized by acidification with trifluoroacetic acid or acetic acid yielding stable dicarbonyl (halo) hydridobis (phosphorus donor)iron(II) complexes (L = P(OMe)3, X = Br (10a), I (10b); L = P(OiPr)3, X = Br (11a), I (11b);L = PEt3, X = Br (12a), I (12b)). In the presence of N2, 8a was transformed into dinitrogen complex [Fe(CO)2{P(OiPr)3}2N2] (13). With 9a,b the reaction led to formation of [Fe‐(CO)2(PEt3)2)2N2] (14) and [{Fe(CO)2‐(PEt3)2}2(μ‐N2)] (15). In solution at low temperature (−90 to 0°C), the dinitrogen complexes 14 and 15 are in equilibrium with each other. Complexes 13, 14, and 15 were characterized by IR, 1H, 13C, 31P, and 15N NMR spectroscopy. The structures of 5a, 6b, 14, and 15 were determined by X‐ray diffraction studies.",
author = "Helmut Kandler and Christine Gauss and Wolfgang Bidell and Stephan Rosenberger and Tobias Burgi and Eremenko, {Igor L.} and Dario Veghini and Olli Orama and Peter Burger and Heinz Berke",
year = "1995",
doi = "10.1002/chem.19950010808",
language = "English",
volume = "1",
pages = "541--548",
journal = "Chemistry - A European Journal",
issn = "0947-6539",
publisher = "Wiley",
number = "8",

}

Kandler, H, Gauss, C, Bidell, W, Rosenberger, S, Burgi, T, Eremenko, IL, Veghini, D, Orama, O, Burger, P & Berke, H 1995, 'The reduction of [Fe(CO)2L2X2] = P(OMe)3, P(OiPr)3, PEt3; x= Br--from iron(II) to iron (0) via stable iron (I) intermediates', Chemistry - A European Journal, vol. 1, no. 8, pp. 541-548. https://doi.org/10.1002/chem.19950010808

The reduction of [Fe(CO)2L2X2] = P(OMe)3, P(OiPr)3, PEt3; x= Br--from iron(II) to iron (0) via stable iron (I) intermediates. / Kandler, Helmut; Gauss, Christine; Bidell, Wolfgang; Rosenberger, Stephan; Burgi, Tobias; Eremenko, Igor L.; Veghini, Dario; Orama, Olli; Burger, Peter; Berke, Heinz (Corresponding Author).

In: Chemistry - A European Journal, Vol. 1, No. 8, 1995, p. 541-548.

Research output: Contribution to journalArticleScientificpeer-review

TY - JOUR

T1 - The reduction of [Fe(CO)2L2X2] = P(OMe)3, P(OiPr)3, PEt3; x= Br--from iron(II) to iron (0) via stable iron (I) intermediates

AU - Kandler, Helmut

AU - Gauss, Christine

AU - Bidell, Wolfgang

AU - Rosenberger, Stephan

AU - Burgi, Tobias

AU - Eremenko, Igor L.

AU - Veghini, Dario

AU - Orama, Olli

AU - Burger, Peter

AU - Berke, Heinz

PY - 1995

Y1 - 1995

N2 - The reduction of [Fe(CO)2‐L2X2] (L = P(OMe)3 X = Br (1a), I (1b); L = P(OiPr)3, X = Br (2a), I (2b); L = PEt3, X = Br (3a), I (3b)) with Zn in dioxane (1a,b‐2a,b) or PhLi in ether (3a,b) led to formation of the corresponding dicarbonyl(halo)bis(phosphorus donor)iron(I) complexes (L = P(OMe)3, X = Br (4a), I (4b); L = P(OiPr)3, X = Br (5a), I (5b); L = PEt3, X = Br (6a), I (6b)). Slightly contaminated 5a,b and pure 6a,b were isolated as stable crystalline blue or blue‐green complexes. Complexes 4a,b were obtained, with only minor impurities, by comproportionation of 1a,b and the dicarbonyl(halo)bis‐(trimethylphosphite)ferrate anions 7a,b and characterized in THF solution. The comproportionation products 5a,b‐6a,b were obtained in high yields by reaction of 2a,b‐3a,b with the dinitrogen complexes 13‐15. Further reduction of 4a,b‐6a,b or exhaustive reduction of 1a,b‐3a,b with sodium amalgam or iBuLi in THF afforded the nonisolable dicarbonyl‐(halo)bis(phosphorus donor)ferrate(o) anions (7a,b‐9a,b). The latter were characterized by acidification with trifluoroacetic acid or acetic acid yielding stable dicarbonyl (halo) hydridobis (phosphorus donor)iron(II) complexes (L = P(OMe)3, X = Br (10a), I (10b); L = P(OiPr)3, X = Br (11a), I (11b);L = PEt3, X = Br (12a), I (12b)). In the presence of N2, 8a was transformed into dinitrogen complex [Fe(CO)2{P(OiPr)3}2N2] (13). With 9a,b the reaction led to formation of [Fe‐(CO)2(PEt3)2)2N2] (14) and [{Fe(CO)2‐(PEt3)2}2(μ‐N2)] (15). In solution at low temperature (−90 to 0°C), the dinitrogen complexes 14 and 15 are in equilibrium with each other. Complexes 13, 14, and 15 were characterized by IR, 1H, 13C, 31P, and 15N NMR spectroscopy. The structures of 5a, 6b, 14, and 15 were determined by X‐ray diffraction studies.

AB - The reduction of [Fe(CO)2‐L2X2] (L = P(OMe)3 X = Br (1a), I (1b); L = P(OiPr)3, X = Br (2a), I (2b); L = PEt3, X = Br (3a), I (3b)) with Zn in dioxane (1a,b‐2a,b) or PhLi in ether (3a,b) led to formation of the corresponding dicarbonyl(halo)bis(phosphorus donor)iron(I) complexes (L = P(OMe)3, X = Br (4a), I (4b); L = P(OiPr)3, X = Br (5a), I (5b); L = PEt3, X = Br (6a), I (6b)). Slightly contaminated 5a,b and pure 6a,b were isolated as stable crystalline blue or blue‐green complexes. Complexes 4a,b were obtained, with only minor impurities, by comproportionation of 1a,b and the dicarbonyl(halo)bis‐(trimethylphosphite)ferrate anions 7a,b and characterized in THF solution. The comproportionation products 5a,b‐6a,b were obtained in high yields by reaction of 2a,b‐3a,b with the dinitrogen complexes 13‐15. Further reduction of 4a,b‐6a,b or exhaustive reduction of 1a,b‐3a,b with sodium amalgam or iBuLi in THF afforded the nonisolable dicarbonyl‐(halo)bis(phosphorus donor)ferrate(o) anions (7a,b‐9a,b). The latter were characterized by acidification with trifluoroacetic acid or acetic acid yielding stable dicarbonyl (halo) hydridobis (phosphorus donor)iron(II) complexes (L = P(OMe)3, X = Br (10a), I (10b); L = P(OiPr)3, X = Br (11a), I (11b);L = PEt3, X = Br (12a), I (12b)). In the presence of N2, 8a was transformed into dinitrogen complex [Fe(CO)2{P(OiPr)3}2N2] (13). With 9a,b the reaction led to formation of [Fe‐(CO)2(PEt3)2)2N2] (14) and [{Fe(CO)2‐(PEt3)2}2(μ‐N2)] (15). In solution at low temperature (−90 to 0°C), the dinitrogen complexes 14 and 15 are in equilibrium with each other. Complexes 13, 14, and 15 were characterized by IR, 1H, 13C, 31P, and 15N NMR spectroscopy. The structures of 5a, 6b, 14, and 15 were determined by X‐ray diffraction studies.

U2 - 10.1002/chem.19950010808

DO - 10.1002/chem.19950010808

M3 - Article

VL - 1

SP - 541

EP - 548

JO - Chemistry - A European Journal

JF - Chemistry - A European Journal

SN - 0947-6539

IS - 8

ER -