Side-on coordination mode of a pyrazolyl group in the structure of a divalent [Sm{B(3-Mepz)<sub>4</sub>}<sub>2</sub>] complex (3-Mepz is 3-methylpyrazol-1-yl)

Arikawa, Yasuhiro; Inada, Kei Ichiro; Onishi, Masayoshi

doi:10.1107/s2053229616011578

Cited by 4 publications

(2 citation statements)

References 20 publications

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“…Due to the substituent changes, the structure symmetry of the compounds rises in the following order Eu(Tp Ph,Me ) 2 → Eu(Tp Ph ) 2 → Eu(Tp Ph2 ) 2 . The latter has a higher symmetry of D 3d , while the others possess a "bent sandwich-like" structure known for other Ln(II) ions [91,[93][94][95][96][97][98]. The complex Eu(Tp Ph ) 2 (4) adopts an ideal trigonal antiprismatic (D 3d symmetry) molecular structure with a linear B-Eu-B fragment (Figure 1).…”

Section: Lanthanide Complexes With Tripodal Ligandsmentioning

confidence: 99%

The Tripodal Ligand’s 4f Complexes: Use in Molecular Magnetism

Vostrikova

2023

Inorganics

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A predictable type of coordination is a key property of tripodal ligands. Homo- and heteroleptic lanthanide complexes with tripodal ligands are a representative class of compounds. However, despite the fact that many of them are paramagnetic, their magnetic behavior is poorly studied. This is because their photophysical and catalytic properties are considered more attractive. In the present review, we try to summarize the available structural information and only a few examples of data on magnetic properties in order to draw some conclusions about the prospect of such ligands in the design of quantum molecular magnets involving lanthanide (Ln) ions. We would also like to catch the reader’s attention to the fact that, despite the consideration of a large part of the currently known Ln compounds with tripodal ligands, this review is not exhaustive. However, our goal is to draw the attention of magnetochemists and theoreticians to a whole niche of air-stable Ln complexes that is still out of their field of vision.

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Section: Lanthanide Complexes With Tripodal Ligandsmentioning

confidence: 99%

The Tripodal Ligand’s 4f Complexes: Use in Molecular Magnetism

Vostrikova

2023

Inorganics

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“…The molecular structure of Eu(Tp Ph2 )2 differs from those of Eu(Tp Ph,Me )2, Eu(Tp Ph )2. Due to the substituents change, the structure symmetry of the compounds rises in the following order Eu(Tp Ph,Me )2 → Eu(Tp Ph )2 → Eu(Tp Ph2 )2, the latter having a higher symmetry of D3d, while the others possess a "bent sandwich-like" structure known for other Ln(II) ions [91,[93][94][95][96][97][98]. The complex Eu(Tp Ph )2 (4) adopts an ideal trigonal antiprismatic (D3d symmetry) molecular structure with a linear B-Eu-B fragment (Figure 1).…”

Section: Complexes With Tris(pyrazolyl)borates Tripodal Ligandsmentioning

confidence: 99%

Lanthanide Complexes with Tripodal Ligands

Vostrikova¹

2023

Preprint

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The main property of tripodal ligands is the predictable type of coordination. Homo- and heteroleptic lanthanide complexes with tripodal ligands are a representative class of compounds. However, despite the fact that many of them are paramagnetic their magnetic behavior is poorly understood. This is because their photophysical and catalytic properties have been more attractive. In the present review, we are trying to summarize the available structural information and extremely few data on magnetic properties in order to draw some conclusions about the prospective of tripods using in the design of quantum molecular magnets based on Ln ions. We would like to draw the reader's attention to the fact that despite the consideration of a large part of the currently known lanthanide compounds with tripodal ligands, this review is not exhaustive. However, our goal was to draw the attention of researchers to the fact that a whole niche of air-stable Ln complexes remained outside the attention of magnetochemists and theoreticians.

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Synthesis and Structure of Alkaline Earth Bis{hydrido-tris(3,5-diisopropyl-pyrazol-1-yl)borate} Complexes: Ae(Tp^iPr2)₂ (Ae = Mg, Ca, Sr, Ba)

et al. 2021

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The synthesis and structural characterization of Ae(TpiPr2)2 (Ae = Mg, Ca, Sr, Ba; TpiPr2 = hydrido-tris(3,5-diisopropyl-pyrazol-1-yl)borate) are reported. In the crystalline state, the alkaline earth metal centers are six-coordinate, even the small Mg2+ ion, with two κ3-N,N′,N′′-Tp iPr2 ligands, disposed in a bent arrangement (B···Ae···B < 180°). However, contrary to the analogous Ln(TpiPr2)2 (Ln = Sm, Eu, Tm, Yb) compounds, which all exhibit a bent-metallocene structure close to C s symmetry, the Ae(TpiPr2)2 compounds exhibit a greater structural variation. The smallest Mg(TpiPr2)2 has crystallographically imposed C 2 symmetry, requiring both bending and twisting of the two Tp iPr2 ligands, while with the similarly sized Ca2+ and Sr2+, the structures are back toward the bent-metallocene C s symmetry. Despite the structural variations, the B···M···B bending angle follows a linear size-dependence for all divalent metal ions going from Mg2+ to Sm2+, decreasing with increasing metal ion size. The complex of the largest metal ion, Ba2+, forms an almost linear structure, B···Ba···B 167.5°. However, the “linearity” is not due to the compound approaching the linear metallocene-like geometry, but is the result of the pyrazolyl groups significantly tipping toward the metal center, approaching “side-on” coordination. An attempt to rationalize the observed structural variations is made.

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Side-on coordination mode of a pyrazolyl group in the structure of a divalent [Sm{B(3-Mepz)₄}₂] complex (3-Mepz is 3-methylpyrazol-1-yl)

Cited by 4 publications

References 20 publications

The Tripodal Ligand’s 4f Complexes: Use in Molecular Magnetism

The Tripodal Ligand’s 4f Complexes: Use in Molecular Magnetism

Lanthanide Complexes with Tripodal Ligands

Synthesis and Structure of Alkaline Earth Bis{hydrido-tris(3,5-diisopropyl-pyrazol-1-yl)borate} Complexes: Ae(Tp^iPr2)₂ (Ae = Mg, Ca, Sr, Ba)

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Side-on coordination mode of a pyrazolyl group in the structure of a divalent [Sm{B(3-Mepz)4}2] complex (3-Mepz is 3-methylpyrazol-1-yl)

Cited by 4 publications

References 20 publications

The Tripodal Ligand’s 4f Complexes: Use in Molecular Magnetism

The Tripodal Ligand’s 4f Complexes: Use in Molecular Magnetism

Lanthanide Complexes with Tripodal Ligands

Synthesis and Structure of Alkaline Earth Bis{hydrido-tris(3,5-diisopropyl-pyrazol-1-yl)borate} Complexes: Ae(TpiPr2)2 (Ae = Mg, Ca, Sr, Ba)

Contact Info

Product

Resources

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Side-on coordination mode of a pyrazolyl group in the structure of a divalent [Sm{B(3-Mepz)₄}₂] complex (3-Mepz is 3-methylpyrazol-1-yl)

Synthesis and Structure of Alkaline Earth Bis{hydrido-tris(3,5-diisopropyl-pyrazol-1-yl)borate} Complexes: Ae(Tp^iPr2)₂ (Ae = Mg, Ca, Sr, Ba)