Reactivity of a Fe(III)-Bound Methoxide Supported with a Tris(thiolato)phosphine Ligand

Activation of C-Cl Bond in CH2Cl2 by Nucleophilic Attack of a Fe(III)-OCH3 Moiety

Kai Chun Chang, Ching Ju Huang, Ya Ho Chang, Zong Han Wu, Ting Shen Kuo, Hua-Fen Hsu

Research output: Contribution to journalArticle

3 Citations (Scopus)

Abstract

Two mononuclear nonheme FeIII complexes, [PPh4][FeIII(PS3′)(OCH3)] (1) and [PPh4][FeIII(PS3′)(Cl)] (2), supported by a tris(benzenethiolato)phosphine derivative PS3′ (PS3′ = P(C6H3-3-Me3Si-2-S)33-) have been synthesized and characterized. The structures resolved from X-ray crystallography show that FeIII centers in both complexes adopt distorted trigonal-bipyramidal geometry with a methoxide or a chloride binding in the axial position. The magnetic data for both are consistent with intermediate-spin FeIII centers with a C3 symmetry (S = 3/2 ground state). The bound methoxide in 1 is labile and can be replaced by a CH3CN molecule. The forming FeIII-CH3CN species can be further reduced by cobaltcene quantitatively to a stable FeII-CH3CN complex, [Fe(PS3′)(CH3CN)]-. One-electron oxidation of 2 by ferrocenium gave a FeIV analogue, [FeIV(PS3′)(Cl)]. Importantly, the FeIII-OCH3 moiety in complex 1 acts as a strong nucleophile that activates the C-Cl bond in CH2Cl2, leading to the formation of complex 2 quantitatively. Complex 1 also reacts with other electrophiles, benzyl chloride and benzyl bromide, to generate FeIII-X species (X = Cl or Br). The reactions were investigated and monitored by UV-vis-NIR, NMR, and ESI-MS spectroscopies.

Original languageEnglish
Pages (from-to)566-572
Number of pages7
JournalInorganic Chemistry
Volume55
Issue number2
DOIs
Publication statusPublished - 2016 Jan 19

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phosphine
Nucleophiles
X ray crystallography
Crystal symmetry
phosphines
Ground state
attack
Chlorides
reactivity
Chemical activation
chlorides
Nuclear magnetic resonance
Spectroscopy
activation
Ligands
Derivatives
Oxidation
ligands
Molecules
Geometry

All Science Journal Classification (ASJC) codes

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry

Cite this

@article{2100a31d7c4d421eba1d82cd32b538c9,
title = "Reactivity of a Fe(III)-Bound Methoxide Supported with a Tris(thiolato)phosphine Ligand: Activation of C-Cl Bond in CH2Cl2 by Nucleophilic Attack of a Fe(III)-OCH3 Moiety",
abstract = "Two mononuclear nonheme FeIII complexes, [PPh4][FeIII(PS3′)(OCH3)] (1) and [PPh4][FeIII(PS3′)(Cl)] (2), supported by a tris(benzenethiolato)phosphine derivative PS3′ (PS3′ = P(C6H3-3-Me3Si-2-S)33-) have been synthesized and characterized. The structures resolved from X-ray crystallography show that FeIII centers in both complexes adopt distorted trigonal-bipyramidal geometry with a methoxide or a chloride binding in the axial position. The magnetic data for both are consistent with intermediate-spin FeIII centers with a C3 symmetry (S = 3/2 ground state). The bound methoxide in 1 is labile and can be replaced by a CH3CN molecule. The forming FeIII-CH3CN species can be further reduced by cobaltcene quantitatively to a stable FeII-CH3CN complex, [Fe(PS3′)(CH3CN)]-. One-electron oxidation of 2 by ferrocenium gave a FeIV analogue, [FeIV(PS3′)(Cl)]. Importantly, the FeIII-OCH3 moiety in complex 1 acts as a strong nucleophile that activates the C-Cl bond in CH2Cl2, leading to the formation of complex 2 quantitatively. Complex 1 also reacts with other electrophiles, benzyl chloride and benzyl bromide, to generate FeIII-X species (X = Cl or Br). The reactions were investigated and monitored by UV-vis-NIR, NMR, and ESI-MS spectroscopies.",
author = "Chang, {Kai Chun} and Huang, {Ching Ju} and Chang, {Ya Ho} and Wu, {Zong Han} and Kuo, {Ting Shen} and Hua-Fen Hsu",
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month = "1",
day = "19",
doi = "10.1021/acs.inorgchem.5b02135",
language = "English",
volume = "55",
pages = "566--572",
journal = "Inorganic Chemistry",
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publisher = "American Chemical Society",
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Reactivity of a Fe(III)-Bound Methoxide Supported with a Tris(thiolato)phosphine Ligand : Activation of C-Cl Bond in CH2Cl2 by Nucleophilic Attack of a Fe(III)-OCH3 Moiety. / Chang, Kai Chun; Huang, Ching Ju; Chang, Ya Ho; Wu, Zong Han; Kuo, Ting Shen; Hsu, Hua-Fen.

In: Inorganic Chemistry, Vol. 55, No. 2, 19.01.2016, p. 566-572.

Research output: Contribution to journalArticle

TY - JOUR

T1 - Reactivity of a Fe(III)-Bound Methoxide Supported with a Tris(thiolato)phosphine Ligand

T2 - Activation of C-Cl Bond in CH2Cl2 by Nucleophilic Attack of a Fe(III)-OCH3 Moiety

AU - Chang, Kai Chun

AU - Huang, Ching Ju

AU - Chang, Ya Ho

AU - Wu, Zong Han

AU - Kuo, Ting Shen

AU - Hsu, Hua-Fen

PY - 2016/1/19

Y1 - 2016/1/19

N2 - Two mononuclear nonheme FeIII complexes, [PPh4][FeIII(PS3′)(OCH3)] (1) and [PPh4][FeIII(PS3′)(Cl)] (2), supported by a tris(benzenethiolato)phosphine derivative PS3′ (PS3′ = P(C6H3-3-Me3Si-2-S)33-) have been synthesized and characterized. The structures resolved from X-ray crystallography show that FeIII centers in both complexes adopt distorted trigonal-bipyramidal geometry with a methoxide or a chloride binding in the axial position. The magnetic data for both are consistent with intermediate-spin FeIII centers with a C3 symmetry (S = 3/2 ground state). The bound methoxide in 1 is labile and can be replaced by a CH3CN molecule. The forming FeIII-CH3CN species can be further reduced by cobaltcene quantitatively to a stable FeII-CH3CN complex, [Fe(PS3′)(CH3CN)]-. One-electron oxidation of 2 by ferrocenium gave a FeIV analogue, [FeIV(PS3′)(Cl)]. Importantly, the FeIII-OCH3 moiety in complex 1 acts as a strong nucleophile that activates the C-Cl bond in CH2Cl2, leading to the formation of complex 2 quantitatively. Complex 1 also reacts with other electrophiles, benzyl chloride and benzyl bromide, to generate FeIII-X species (X = Cl or Br). The reactions were investigated and monitored by UV-vis-NIR, NMR, and ESI-MS spectroscopies.

AB - Two mononuclear nonheme FeIII complexes, [PPh4][FeIII(PS3′)(OCH3)] (1) and [PPh4][FeIII(PS3′)(Cl)] (2), supported by a tris(benzenethiolato)phosphine derivative PS3′ (PS3′ = P(C6H3-3-Me3Si-2-S)33-) have been synthesized and characterized. The structures resolved from X-ray crystallography show that FeIII centers in both complexes adopt distorted trigonal-bipyramidal geometry with a methoxide or a chloride binding in the axial position. The magnetic data for both are consistent with intermediate-spin FeIII centers with a C3 symmetry (S = 3/2 ground state). The bound methoxide in 1 is labile and can be replaced by a CH3CN molecule. The forming FeIII-CH3CN species can be further reduced by cobaltcene quantitatively to a stable FeII-CH3CN complex, [Fe(PS3′)(CH3CN)]-. One-electron oxidation of 2 by ferrocenium gave a FeIV analogue, [FeIV(PS3′)(Cl)]. Importantly, the FeIII-OCH3 moiety in complex 1 acts as a strong nucleophile that activates the C-Cl bond in CH2Cl2, leading to the formation of complex 2 quantitatively. Complex 1 also reacts with other electrophiles, benzyl chloride and benzyl bromide, to generate FeIII-X species (X = Cl or Br). The reactions were investigated and monitored by UV-vis-NIR, NMR, and ESI-MS spectroscopies.

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U2 - 10.1021/acs.inorgchem.5b02135

DO - 10.1021/acs.inorgchem.5b02135

M3 - Article

VL - 55

SP - 566

EP - 572

JO - Inorganic Chemistry

JF - Inorganic Chemistry

SN - 0020-1669

IS - 2

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