Dataset Information

High-Spin Iron(VI), Low-Spin Ruthenium(VI), and Magnetically Bistable Osmium(VI) in Molecular Group 8 Nitrido Trifluorides NMF₃.

ABSTRACT: Pseudo-tetrahedral nitrido trifluorides N≡MF₃ (M=Fe, Ru, Os) and square pyramidal nitrido tetrafluorides N≡MF₄ (M=Ru, Os) were formed by free-metal-atom reactions with NF₃ and subsequently isolated in solid neon at 5 K. Their IR spectra were recorded and analyzed aided by quantum-chemical calculations. For a d² electron configuration of the N≡MF₃ compounds in C_3v symmetry, Hund's rule predict a high-spin ³ A₂ ground state with two parallel spin electrons and two degenerate metal d(δ)-orbitals. The corresponding high-spin ³ A₂ ground state was, however, only found for N≡FeF₃ , the first experimentally verified neutral nitrido Fe^VI species. The valence-isoelectronic N≡RuF₃ and N≡OsF₃ adopt different angular distorted singlet structures. For N≡RuF₃ , the triplet ³ A₂ state is only 5 kJ mol^-1 higher in energy than the singlet ¹ A' ground state, and the magnetically bistable molecular N≡OsF₃ with two distorted near degenerate ¹ A' and ³ A" electronic states were experimentally detected at 5 K in solid neon.

SUBMITTER: Stuker T

PROVIDER: S-EPMC8457171 | biostudies-literature | 2021 Aug

REPOSITORIES: biostudies-literature

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Publications

High-Spin Iron(VI), Low-Spin Ruthenium(VI), and Magnetically Bistable Osmium(VI) in Molecular Group 8 Nitrido Trifluorides NMF3.

Stüker Tony T Xia Xiya X Beckers Helmut H Riedel Sebastian S

Chemistry (Weinheim an der Bergstrasse, Germany) 20210626 45

Pseudo-tetrahedral nitrido trifluorides N≡MF3 (M=Fe, Ru, Os) and square pyramidal nitrido tetrafluorides N≡MF4 (M=Ru, Os) were formed by free-metal-atom reactions with NF3 and subsequently isolated in solid neon at 5 K. Their IR spectra were recorded and analyzed aided by quantum-chemical calculations. For a d2 electron configuration of the N≡MF3 compounds in C3v symmetry, Hund's rule predict a high-spin 3 A2 ...[more]

PMID: 34043842

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Project description:The transmembrane protein known as the mitochondrial calcium uniporter (MCU) mediates the influx of calcium ions (Ca2+) into the mitochondrial matrix. An overload of mitochondrial Ca2+ ( m Ca2+) is directly linked to damaging effects in pathological conditions. Therefore, inhibitors of the MCU are important chemical biology tools and therapeutic agents. Here, two new analogues of previously reported Ru- and Os-based MCU inhibitors Ru265 and Os245, of the general formula [(C10H15CO2)M(NH3)4(μ-N)M(NH3)4(O2CC10H15)](CF3SO3)3, where M = Ru (1) or Os (2), are reported. These analogues bear adamantane functional groups, which were installed to act as guests for the host molecule cucurbit-[7]-uril (CB[7]). These complexes were characterized and analyzed for their efficiency as guests for CB[7]. As shown through a variety of spectroscopic techniques, each adamantane ligand is encapsulated into one CB[7], affording a supramolecular complex of 1 : 2 stoichiometry. The biological effects of these compounds in the presence and absence of two equiv. CB[7] were assessed. Both complexes 1 and 2 exhibit enhanced cellular uptake compared to the parent compounds Ru265 and Os245, and their uptake is increased further in the presence of CB[7]. Compared to Ru265 and Os245, 1 and 2 are less potent as m Ca2+ uptake inhibitors in permeabilized cell models. However, in intact cell systems, 1 and 2 inhibit the MCU at concentrations as low as 1 μM, marking an advantage over Ru265 and Os245 which require an order of magnitude higher doses for similar biological effects. The presence of CB[7] did not affect the inhibitory properties of 1 and 2. Experiments in primary cortical neurons showed that 1 and 2 can elicit protective effects against oxygen-glucose deprivation at lower doses than those required for Ru265 or Os245. At low concentrations, the protective effects of 1 were modulated by CB[7], suggesting that supramolecular complex formation can play a role in these biological conditions. The in vivo biocompatibility of 1 was investigated in mice. The intraperitoneal administration of these compounds and their CB[7] complexes led to time-dependent induction of seizures with no protective effects elicited by CB[7]. This work demonstrates the potential for supramolecular interactions in the development of MCU inhibitors.

Dataset Information

High-Spin Iron(VI), Low-Spin Ruthenium(VI), and Magnetically Bistable Osmium(VI) in Molecular Group 8 Nitrido Trifluorides NMF₃.

Publications

High-Spin Iron(VI), Low-Spin Ruthenium(VI), and Magnetically Bistable Osmium(VI) in Molecular Group 8 Nitrido Trifluorides NMF<sub>3</sub>.

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