<scp>Ammonium‐Iron</scp>(<scp>III</scp>) metallacryptate inclusion complexes based on Aroylbis(<i>N</i>,<i>N</i>‐diethylthioureas): Synthesis and structure

Huy, Nguyen Hung; Abram, Ulrich; Thang, Pham Chien

doi:10.1002/vjch.202100206

Vietnam Journal of Chemistry

2022

DOI: 10.1002/vjch.202100206

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Ammonium‐Iron(III) metallacryptate inclusion complexes based on Aroylbis(N,N‐diethylthioureas): Synthesis and structure

Nguyen Hung Huy,

Ulrich Abram,

Pham Chien Thang

Abstract: One‐pot reactions of pyridine‐ or catechol‐scaffolding aroylbis(N,N‐diethylthioureas), H2L1 or H2L2, with methanolic solutions of FeCl3 and NH4Cl bring about novel cationic ammonium‐inclusion complexes {NH4 ⊂ [Fe2(L)3]}+ (L = L1 or L2), which could be separated as PF6– salts. The inclusion compounds have been characterized by elemental analyses and spectroscopic methods such as HRMS, IR and SCXRD. Ammonium ions are captured in the intramolecular voids of {2}‐metallacryptands {[Fe2(L)3]} (L = L1 or L2) resultin… Show more

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Cited by 3 publications

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Organotellurium(II) and ‐(IV) Compounds with Picolinoylbis(thioureas): From Simple 1 : 1 Adducts to Multimetallic Aggregates

dos Santos,

Schwade,

Lang

et al. 2024

Eur J Inorg Chem

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Reactions of 2,6‐dipicolinoylbis(N,N‐diethylthiourea) (H2LEt) with common tellurium(IV) starting materials such as PhTeBr3 or TeBr4 yield various tellurium(IV) and tellurium(II) compounds depending on the conditions applied. Equimolar amounts of H2LEt and PhTeBr3 give the 1:1 complex [PhTeIVBr3(H2LEt)], while with an excess of H2LEt, the tellurium compound is partially reduced and a {PhTeII}+ building block coordinates to both sulfur atoms of H2LEt under formation of the ion pair [PhTeII(H2LEt)][PhTeIVBr4]. Similar reactions between H2LEt and TeBr4 give the neutral monomer [TeIIBr2(H2LEt)] or the coordination polymer [TeIIBr2(H2LEt)]∞. The latter compound is also formed with the assistance of Pb2+ ions. While the lead ions do not appear in the isolated product, similar reactions with transition metal ions such as Ni2+, Mn2+, or Co2+ result in the formation of heterobimetallic complexes, in which Te(II) building blocks are directed to the sulfur atoms of the deprotonated ligand {H2LEt2‐S,S}2‐, while the transition metal ions occupy central coordination positions between two of the organic ligands using the pyridine nitrogen atom, carbonyl oxygen atom(s) and/or the nitrogen atoms of the thiourea units.

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Organotellurium(II) and ‐(IV) Compounds with Picolinoylbis(thioureas): From Simple 1 : 1 Adducts to Multimetallic Aggregates

dos Santos,

Schwade,

Lang

et al. 2024

Eur J Inorg Chem

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Gold-Based Coronands as Hosts for M3+ Metal Ions: Ring Size Matters

Sucena,

Demirer,

Baitullina

et al. 2023

Molecules

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The controlled, self-assembled synthesis of multinuclear coordination compounds can be performed via different approaches. Frequently, steric, geometric and/or electronic factors located at the ligand systems predefine the way in which metal ions can assemble them to large aggregates. For the compounds in the present paper, also the Pearson’s acidities and preferred coordination geometries of the metal ions were used as organization principles. The ligand under study, 2,6-dipicolinoylbis(N,N-diethylthiourea), H2L1ethyl, possesses ‘soft’ sulfur and ‘hard’ nitrogen and oxygen donors. One-pot reactions of this compound with [AuCl(tht)] (tht = tetrahydrothiophene) and M3+ salts (M = Sc, Y, La, Ln, Ga, In) give products with gold-based {Au3(L1ethyl)3}3+ or {Au2(L1ethyl)2}2+ coronands, which host central M3+ ions. The formation of such units is templated by the M3+ ions and the individual size of the coronand rings is dependent on the ionic radii of the central ions in a way that small ions such as Ga3+ form a [Ga⊂{Au2(L1ethyl)2}]+ assembly, while larger ions (starting from Sc3+/In3+) establish neutral [M⊂{Au3(L1ethyl)3}] units with nine-coordinate central ions.

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Bimetallic Uranium Complexes with 2,6-Dipicolinoylbis(N,N-Dialkylthioureas)

Njiki Noufele,

Schulze,

Roca Jungfer

et al. 2024

Molecules

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2,6-Dipicolinoylbis(N,N-dialkylthioureas), H2LR, readily react with uranyl salts under formation of monomeric or dimeric complexes of the compositions [UO2(LR)(solv)] (solv = donor solvents such as H2O, MeOH or DMF) or [{UO2(LR)(µ-OMe)}2]2− (1). In such complexes, the uranyl ions are exclusively coordinated by the “hard” O,N,O or N,N,N donor atom sets of the central ligand unit and the lateral sulfur donor atoms do not participate in the coordination. Different conformations have been found for the dimeric anions. The bridging methanolato ligands and the four uncoordinated sulfur atoms can adopt different orientations with respect to the equatorial coordination spheres of the uranyl units. The presence of non-coordinated sulfur atoms offers the opportunity for the coordination of additional, preferably “soft” metal ions. Thus, reactions with [AuCl(PPh3)], lead acetate or acetates of transition metal ions such as Ni2+, Co2+, Fe2+, Mn2+, Zn2+, or Cd2+, were considered for the syntheses of bimetallic complexes. Various oligometallic complexes with uranyl units were prepared: [{UO2(LR)(μ-OMe)(Au(PPh3)}2] (2), [(UO2)3Pb2(LR)4(MeOH)2(μ-OMe)2] (3), [M{UO2(LR)(OAc)}2] (M= Zn, Ni, Co, Fe, Mn or Cd) (R = Et: 5, RR = morph: 6), or [(UO2)(NiI)2(LR)2] (7). The products were extensively studied spectroscopically and by X-ray diffraction.

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Ammonium‐Iron(III) metallacryptate inclusion complexes based on Aroylbis(N,N‐diethylthioureas): Synthesis and structure

Cited by 3 publications

References 27 publications

Organotellurium(II) and ‐(IV) Compounds with Picolinoylbis(thioureas): From Simple 1 : 1 Adducts to Multimetallic Aggregates

Organotellurium(II) and ‐(IV) Compounds with Picolinoylbis(thioureas): From Simple 1 : 1 Adducts to Multimetallic Aggregates

Gold-Based Coronands as Hosts for M3+ Metal Ions: Ring Size Matters

Bimetallic Uranium Complexes with 2,6-Dipicolinoylbis(N,N-Dialkylthioureas)

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