Recent studies on the magnetic properties of paramagnetic metals linked by diamagnetic second metals

Uemura, Kazuhiro; Takamori, Atsushi

doi:10.1016/j.ccr.2022.214736

Cited by 7 publications

(2 citation statements)

References 73 publications

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“…[38,39] Despite going relatively overlooked, understanding these equatorial interactions may offer an effective means to fine-tune the electronic behavior and properties of such complexes. For instance, previous studies focusing on changing the nature of equatorial bidentate ligands show a strong effect on the magnetism, [40] stabilized unusual metal-metal bonds, [41] or improved the reactivity of such complexes. [42,43] Here we present a series of Ru 2 5+ compounds that defies the torsion angle rule.…”

Section: Introductionmentioning

confidence: 99%

Torsion Effects Beyond the δ Bond and the Role of π Metal‐Ligand Interactions

Inchausti,

Mollfulleda,

Swart

et al. 2024

Advanced Science

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Previous studies on bimetallic paddlewheel compounds have established a direct correlation between metal–metal distance and ligand torsion angles, leading to the rule that higher torsion results in longer metal‐metal bond distances. Here, the new discovery based on diarylformamidinate Ru₂⁵⁺ paddlewheel compounds [Ru2Cl(DArF)4] that show an opposite behavior is reported: higher torsions lead to shorter metal–metal distances. This discovery challenges the assumption that internal rotation solely impacts the δ bond. By combining experimental and theoretical techniques, it is demostrated that this trend is associated with previously overlooked π metal‐ligand interactions. These π metal‐ligand interactions are a direct consequence of the paddlewheel structure and the conjugated nature of the bidentate ligands. This findings offer far‐reaching insights into the influence of equatorial ligands and their π‐conjugation characteristics on the electronic properties of paddlewheel complexes. That this effect is not exclusive of diruthenium compounds but also occurs in other bimetallic cores such as ditungsten or dirhodium is demonstrated, and with other ligands showing allyl type conjugation. These results provide a novel approach for fine‐tuning the properties of these compounds with significant implications for materials design.

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Section: Introductionmentioning

confidence: 99%

Torsion Effects Beyond the δ Bond and the Role of π Metal‐Ligand Interactions

Inchausti,

Mollfulleda,

Swart

et al. 2024

Advanced Science

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“…7 In particular, the morphology of the polymer precursor is variable due to its flexible connection characteristics, which can be designed in various configurations according to the different targets. 8 Further, silicon dioxide is usually employed as a support to construct metal-support materials owing to its size, which can be controlled, and abundant sources. 9 Therefore, combining the merits of polymer and SiO 2 to design the metal-supported catalyst for enhancing the performance of the CO 2 cycloaddition with epoxides may be an efficient strategy.…”

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Palladium particles dispersed on hollow structural support improve CO₂conversion

Changsong,

Xu,

Suo

et al. 2023

Chem. Commun.

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Antiferromagnetic Interactions through the Thirteen Å Metal–Metal Distances in Heterometallic One‐Dimensional Chains

Uemura,

Adachi,

Takamori

et al. 2024

Angewandte Chemie

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A heterometallic and paramagnetic one‐dimensional aligned chain in –Rh(+2)–Rh(+2)–Pt(+2)–Ni(+2)–Pt(+2)– with direct metal–metal bonds was obtained via HOMO–LUMO interactions at the σ* (dz2) orbital between [Rh2(O2CCH3)4] and [Pt2Ni(piam)4(NH3)4] (piam = pivalamidate). The one‐dimensional chains had straight backbones attributed to face‐to‐face stacking of each complex, and the Ni atoms were separated by approximately 13 Å from four different metals. Each Ni atom had two unpaired electrons in the d‐orbitals, which strongly exchanged with J = –37.9 cm–1 through the diamagnetic –Pt–Rh–Rh–Pt– bonds.

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Recent studies on the magnetic properties of paramagnetic metals linked by diamagnetic second metals

Cited by 7 publications

References 73 publications

Torsion Effects Beyond the δ Bond and the Role of π Metal‐Ligand Interactions

Torsion Effects Beyond the δ Bond and the Role of π Metal‐Ligand Interactions

Palladium particles dispersed on hollow structural support improve CO₂conversion

Antiferromagnetic Interactions through the Thirteen Å Metal–Metal Distances in Heterometallic One‐Dimensional Chains

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Recent studies on the magnetic properties of paramagnetic metals linked by diamagnetic second metals

Cited by 7 publications

References 73 publications

Torsion Effects Beyond the δ Bond and the Role of π Metal‐Ligand Interactions

Torsion Effects Beyond the δ Bond and the Role of π Metal‐Ligand Interactions

Palladium particles dispersed on hollow structural support improve CO2conversion

Antiferromagnetic Interactions through the Thirteen Å Metal–Metal Distances in Heterometallic One‐Dimensional Chains

Contact Info

Product

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Palladium particles dispersed on hollow structural support improve CO₂conversion