Tuning the Condensation Degree of {FeIII n} Oxo Clusters via Ligand Metathesis, Temperature, and Solvents

Botezat Olga; Van Leusen Jan; Kogerler Paul; Baca Svetlana

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BOTEZAT, Olga, VAN LEUSEN, Jan, KOGERLER, Paul, BACA, Svetlana. Tuning the Condensation Degree of {FeIII n} Oxo Clusters via Ligand Metathesis, Temperature, and Solvents. In: Inorganic Chemistry, 2018, vol. 57, pp. 7904-7913. ISSN 0020-1669. DOI: https://doi.org/10.1021/acs.inorgchem.8b00994

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Inorganic Chemistry

Volumul 57 / 2018 / ISSN 0020-1669

Tuning the Condensation Degree of {Fe^III _n} Oxo Clusters via Ligand Metathesis, Temperature, and Solvents

DOI:https://doi.org/10.1021/acs.inorgchem.8b00994

Pag. 7904-7913

Botezat Olga¹², Van Leusen Jan², Kogerler Paul², Baca Svetlana¹

¹ Institute of Applied Physics, Academy of Sciences of Moldova,
² Institutul de Chimie Anorganică

Disponibil în IBN: 8 august 2018

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Trinuclear μ₃-oxo-centered iron(III) isobutyrate clusters readily react with polyalcohol organic ligands under one-pot synthesis conditions. Depending on the ligand, solvent, and temperature, a range of hexa-, dodeca-, and doicosanuclear iron(III) oxo-hydroxo condensation products, isolated as (mdeaH₃)₂[Fe₆O(thme)₄Cl₆]·0.5(MeCN)·0.5(H₂O) (1), [Fe₁₂O₄(OH)₂(teda)₄(N₃)₄(MeO)₄]N₃(NO₃)_0.5(MeO)_0.5·2.5(H₂O) (2), [Fe₁₂O₆(teda)₄Cl₈]·6(CHCl₃) (3), [Fe₂₂O₁₆(OH)₂(O₂CCHMe₂)₁₈(bdea)₆(EtO)₂(H₂O)₂]·2(EtOH)·5(MeCN)·6(H₂O) (4), and [Fe₂₂O₁₄(OH)₄(O₂CCHMe₂)₁₈(mdea)₆(EtO)₂(H₂O)₂](NO₃)₂·EtOH·H₂O (5), where tedaH₄ = N,N,N′,N′-tetrakis(2-hydroxyethyl)ethylenediamine; thmeH₃ = 1,1,1-tris(hydroxymethyl)ethane; mdeaH₂ = N-methyldiethanolamine; and bdeaH₂ = N-butyldiethanolamine. Complete carboxylate metathesis in the {Fe₃} precursor complexes by thme^3- or teda^4- and the agglomeration of the formed species under solvothermal conditions afforded carboxylate-free {Fe₆} product (1) in MeCN/CH₂Cl₂ or {Fe₁₂} complexes (2 and 3) in MeOH/EtOH and CHCl₃/thf, respectively (thf = tetrahydrofuran). Single-crystal X-ray diffraction analyses revealed that 1 contains a [Fe₆O(thme)₄Cl₆]^2- cluster anion with a Lindqvist-type {Fe₆(μ₆-O)} core motif, charge-compensated by two protonated mdeaH₃ ⁺ cations. 2 comprises a [Fe₁₂O₄(OH)₂(teda)₄(N₃)₄(MeO)₄]²⁺ cation with a {Fe₁₂O₄(OH)₂}²⁶⁺ core, whereas 3 contains a charge-neutral [Fe₁₂O₆(teda)₄(Cl)₈] complex with an {Fe₁₂O₆}²⁴⁺ core. Finally, employing flexible bdeaH₂ or mdeaH₂ ligands under soft reaction conditions afforded giant {Fe₂₂} oxo-hydroxo complexes (4 and 5) with a central {Fe₆} layer sandwiched between two outer {Fe₈} groups. Magnetic studies of 1-5 revealed strong antiferromagnetic coupling between the Fe^III spin centers in all clusters.

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<title xml:lang='en'>Tuning the Condensation Degree of {FeIII n} Oxo Clusters via Ligand Metathesis, Temperature, and Solvents</title>
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<description xml:lang='en' descriptionType='Abstract'><p>Trinuclear &mu;<sub>3</sub>-oxo-centered iron(III) isobutyrate clusters readily react with polyalcohol organic ligands under one-pot synthesis conditions. Depending on the ligand, solvent, and temperature, a range of hexa-, dodeca-, and doicosanuclear iron(III) oxo-hydroxo condensation products, isolated as (mdeaH<sub>3</sub>)<sub>2</sub>[Fe<sub>6</sub>O(thme)<sub>4</sub>Cl<sub>6</sub>]&middot;0.5(MeCN)&middot;0.5(H<sub>2</sub>O) (1), [Fe<sub>12</sub>O<sub>4</sub>(OH)<sub>2</sub>(teda)<sub>4</sub>(N<sub>3</sub>)<sub>4</sub>(MeO)<sub>4</sub>]N<sub>3</sub>(NO<sub>3</sub>)<sub>0.5</sub>(MeO)<sub>0.5</sub>&middot;2.5(H<sub>2</sub>O) (2), [Fe<sub>12</sub>O<sub>6</sub>(teda)<sub>4</sub>Cl<sub>8</sub>]&middot;6(CHCl<sub>3</sub>) (3), [Fe<sub>22</sub>O<sub>16</sub>(OH)<sub>2</sub>(O<sub>2</sub>CCHMe<sub>2</sub>)<sub>18</sub>(bdea)<sub>6</sub>(EtO)<sub>2</sub>(H<sub>2</sub>O)<sub>2</sub>]&middot;2(EtOH)&middot;5(MeCN)&middot;6(H<sub>2</sub>O) (4), and [Fe<sub>22</sub>O<sub>14</sub>(OH)<sub>4</sub>(O<sub>2</sub>CCHMe<sub>2</sub>)<sub>18</sub>(mdea)<sub>6</sub>(EtO)<sub>2</sub>(H<sub>2</sub>O)<sub>2</sub>](NO<sub>3</sub>)<sub>2</sub>&middot;EtOH&middot;H<sub>2</sub>O (5), where tedaH<sub>4</sub> = N,N,N&prime;,N&prime;-tetrakis(2-hydroxyethyl)ethylenediamine; thmeH<sub>3</sub> = 1,1,1-tris(hydroxymethyl)ethane; mdeaH<sub>2</sub> = N-methyldiethanolamine; and bdeaH<sub>2</sub> = N-butyldiethanolamine. Complete carboxylate metathesis in the {Fe<sub>3</sub>} precursor complexes by thme<sup>3-</sup> or teda<sup>4-</sup> and the agglomeration of the formed species under solvothermal conditions afforded carboxylate-free {Fe<sub>6</sub>} product (1) in MeCN/CH<sub>2</sub>Cl<sub>2</sub> or {Fe<sub>12</sub>} complexes (2 and 3) in MeOH/EtOH and CHCl<sub>3</sub>/thf, respectively (thf = tetrahydrofuran). Single-crystal X-ray diffraction analyses revealed that 1 contains a [Fe<sub>6</sub>O(thme)<sub>4</sub>Cl<sub>6</sub>]<sup>2-</sup> cluster anion with a Lindqvist-type {Fe<sub>6</sub>(&mu;<sub>6</sub>-O)} core motif, charge-compensated by two protonated mdeaH<sub>3</sub> <sup>+</sup> cations. 2 comprises a [Fe<sub>12</sub>O<sub>4</sub>(OH)<sub>2</sub>(teda)<sub>4</sub>(N<sub>3</sub>)<sub>4</sub>(MeO)<sub>4</sub>]<sup>2+</sup> cation with a {Fe<sub>12</sub>O<sub>4</sub>(OH)<sub>2</sub>}<sup>26+</sup> core, whereas 3 contains a charge-neutral [Fe<sub>12</sub>O<sub>6</sub>(teda)<sub>4</sub>(Cl)<sub>8</sub>] complex with an {Fe<sub>12</sub>O<sub>6</sub>}<sup>24+</sup> core. Finally, employing flexible bdeaH<sub>2</sub> or mdeaH<sub>2</sub> ligands under soft reaction conditions afforded giant {Fe<sub>22</sub>} oxo-hydroxo complexes (4 and 5) with a central {Fe<sub>6</sub>} layer sandwiched between two outer {Fe<sub>8</sub>} groups. Magnetic studies of 1-5 revealed strong antiferromagnetic coupling between the Fe<sup>III</sup> spin centers in all clusters.</p></description>
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