Versatile Coordination Behavior of the Asymmetric Bis(3‐mesityl‐pyrazol‐1‐yl)(5‐mesitylpyrazol‐1‐yl) Hydroborate Ligand towards Late 3 d M2+ Ions

Versatile Coordination Behavior of the Asymmetric Bis(3‐mesityl‐pyrazol‐1‐yl)(5‐mesitylpyrazol‐1‐yl) Hydroborate Ligand towards Late 3 d M2+ Ions

Bearing in mind the potential which tris(pyrazolyl) hydroborate ligands have demonstrated in various different fields of coordination chemistry, the behavior of a more rarely employed representative, namely bis(3‐mesitylpyrazol‐1‐yl)(5‐mesitylpyrazol‐1‐yl) hydroborate (TpMes,H*), towards a series of...

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Published in:European journal of inorganic chemistry 2021-01, Vol.2021 (1), p.71-85
Main Authors: Müller, Lars, Nadurata, Vincent L., Cula, Beatrice, Hoof, Santina, Herwig, Christian, Limberg, Christian
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Language:eng
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First row metal
Ligand
rearrangement
Structure
Tris(pyrazolyl)borate
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recordid cdi_wiley_primary_10_1002_ejic_202000895_EJIC202000895
title Versatile Coordination Behavior of the Asymmetric Bis(3‐mesityl‐pyrazol‐1‐yl)(5‐mesitylpyrazol‐1‐yl) Hydroborate Ligand towards Late 3 d M2+ Ions
format Article
creator Müller, Lars
Nadurata, Vincent L.
Cula, Beatrice
Hoof, Santina
Herwig, Christian
Limberg, Christian
subjects First row metal
Ligand
rearrangement
Structure
Tris(pyrazolyl)borate
ispartof European journal of inorganic chemistry, 2021-01, Vol.2021 (1), p.71-85
description Bearing in mind the potential which tris(pyrazolyl) hydroborate ligands have demonstrated in various different fields of coordination chemistry, the behavior of a more rarely employed representative, namely bis(3‐mesitylpyrazol‐1‐yl)(5‐mesitylpyrazol‐1‐yl) hydroborate (TpMes,H*), towards a series of divalent metal ions has been investigated. Thus, the synthesis of two new heteroleptic metal chlorido [TpMes,H*MCl] complexes, 2, (Mn2+, 2‐a, and Cu2+, 2‐e) are described, which correspond to the typical precursor compounds that would be needed for subsequent research. Structural and spectroscopic properties of the two new and four published members of this series (M=Fe2+, 2‐b, Co2+, 2‐c, Ni2+, 2‐d, Zn2+, 2‐f) are discussed in detail for the solid and solution states. Furthermore, synthetic routes to five homoleptic [(TpMes,H*)2M] complexes, 3, bearing Mn2+, 3‐a, Fe2+, 3‐b, Co2+, 3‐c, Ni2+, 3‐d, and Cu2+, 3‐e, ions as well as an alternative preparation method for [(κ2‐TpMes,H*)2Zn], 3‐f, are described. Their structures and spectroscopic parameters are compared to those of their heteroleptic counterparts. Additionally, the complex [(TpH,Mes*)2Cu], 4, is reported, representing the second example of a complex with the (3‐mesitylpyrazol‐1‐yl)bis(5‐mesitylpyrazol‐1‐yl) hydroborate ligand (TpH,Mes*). The coordination behavior of TpMes,H* – a so far rarely employed but rather versatile tris(pyrazol‐1‐yl) hydroborate ligand – towards divalent late 3d metal ions were investigated structurally and spectroscopically. Heteroleptic metal halide [TpMes,H*MCl] and homoleptic complexes [(TpMes,H*)2M] thus gained provided insights about the steric conditions the ligand requires and brings about. Moreover, new structural motifs were discovered and thermochromism was revealed for two complexes.
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source Wiley Online Library Journals; Wiley Open Access Journals
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Thus, the synthesis of two new heteroleptic metal chlorido [TpMes,H*MCl] complexes, 2, (Mn2+, 2‐a, and Cu2+, 2‐e) are described, which correspond to the typical precursor compounds that would be needed for subsequent research. Structural and spectroscopic properties of the two new and four published members of this series (M=Fe2+, 2‐b, Co2+, 2‐c, Ni2+, 2‐d, Zn2+, 2‐f) are discussed in detail for the solid and solution states. Furthermore, synthetic routes to five homoleptic [(TpMes,H*)2M] complexes, 3, bearing Mn2+, 3‐a, Fe2+, 3‐b, Co2+, 3‐c, Ni2+, 3‐d, and Cu2+, 3‐e, ions as well as an alternative preparation method for [(κ2‐TpMes,H*)2Zn], 3‐f, are described. Their structures and spectroscopic parameters are compared to those of their heteroleptic counterparts. Additionally, the complex [(TpH,Mes*)2Cu], 4, is reported, representing the second example of a complex with the (3‐mesitylpyrazol‐1‐yl)bis(5‐mesitylpyrazol‐1‐yl) hydroborate ligand (TpH,Mes*). 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Thus, the synthesis of two new heteroleptic metal chlorido [TpMes,H*MCl] complexes, 2, (Mn2+, 2‐a, and Cu2+, 2‐e) are described, which correspond to the typical precursor compounds that would be needed for subsequent research. Structural and spectroscopic properties of the two new and four published members of this series (M=Fe2+, 2‐b, Co2+, 2‐c, Ni2+, 2‐d, Zn2+, 2‐f) are discussed in detail for the solid and solution states. Furthermore, synthetic routes to five homoleptic [(TpMes,H*)2M] complexes, 3, bearing Mn2+, 3‐a, Fe2+, 3‐b, Co2+, 3‐c, Ni2+, 3‐d, and Cu2+, 3‐e, ions as well as an alternative preparation method for [(κ2‐TpMes,H*)2Zn], 3‐f, are described. Their structures and spectroscopic parameters are compared to those of their heteroleptic counterparts. Additionally, the complex [(TpH,Mes*)2Cu], 4, is reported, representing the second example of a complex with the (3‐mesitylpyrazol‐1‐yl)bis(5‐mesitylpyrazol‐1‐yl) hydroborate ligand (TpH,Mes*). 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Thus, the synthesis of two new heteroleptic metal chlorido [TpMes,H*MCl] complexes, 2, (Mn2+, 2‐a, and Cu2+, 2‐e) are described, which correspond to the typical precursor compounds that would be needed for subsequent research. Structural and spectroscopic properties of the two new and four published members of this series (M=Fe2+, 2‐b, Co2+, 2‐c, Ni2+, 2‐d, Zn2+, 2‐f) are discussed in detail for the solid and solution states. Furthermore, synthetic routes to five homoleptic [(TpMes,H*)2M] complexes, 3, bearing Mn2+, 3‐a, Fe2+, 3‐b, Co2+, 3‐c, Ni2+, 3‐d, and Cu2+, 3‐e, ions as well as an alternative preparation method for [(κ2‐TpMes,H*)2Zn], 3‐f, are described. Their structures and spectroscopic parameters are compared to those of their heteroleptic counterparts. Additionally, the complex [(TpH,Mes*)2Cu], 4, is reported, representing the second example of a complex with the (3‐mesitylpyrazol‐1‐yl)bis(5‐mesitylpyrazol‐1‐yl) hydroborate ligand (TpH,Mes*). The coordination behavior of TpMes,H* – a so far rarely employed but rather versatile tris(pyrazol‐1‐yl) hydroborate ligand – towards divalent late 3d metal ions were investigated structurally and spectroscopically. Heteroleptic metal halide [TpMes,H*MCl] and homoleptic complexes [(TpMes,H*)2M] thus gained provided insights about the steric conditions the ligand requires and brings about. Moreover, new structural motifs were discovered and thermochromism was revealed for two complexes.</abstract><doi>10.1002/ejic.202000895</doi><tpages>15</tpages><orcidid>https://orcid.org/0000-0002-0751-1386</orcidid><oa>free_for_read</oa></addata></record>