Room-Temperature-Stable Magnesium Electride via Ni(II) Reduction

Abstract

Herein, we report the synthesis of highly reduced bipyridyl magnesium complexes and the first example of a stable organic magnesium electride supported by quantum mechanical computations and X-ray diffraction. These complexes serve as unconventional homogeneous reductants due to their high solubility, modular redox potentials, and formation of insoluble, non-coordinating byproducts. The applicability of these reductants is showcased by accessing low-valent (bipy) 2 Ni(0) species that are challenging to access otherwise.

Cationic Gold(II) Complexes: Experimental and Theoretical Study**

“…The oxidation state of an electropositive element in contact with elements that are more electronegative can be defined as the difference between its atomic number and its LI A . [73] This quantity is consistent with the IUPAC definition of the oxidation state that is atomic charge after ''ionic approximation" of the heteronuclear bonds. The QTAIM analysis of [M(bipy)(X)] + (M = Cu, Au; X = Cl, Br, I) complexes in Table 4 shows that while the atomic charges of M vary from 0.4 for [Au(bipy)(I)] + to 0.9 for [Cu(bipy)(Cl)] + , the LI M index remains rather constant among all species, confirming the II oxidation state of the metal.…”

Highly oxidized U(vi) within the smallest fullerene: gas-phase synthesis and computational study of boron-doped U@C27B

“…Localization index (LI), a QTAIM-based index that defines the population of an atomic basin minus the shared electrons, has been used recently to measure the oxidation state of electropositive atoms. 44,45 The difference between the LI and atomic number provides a measure of the charge of an atom after the ionic approximation for heteroatomic bonds, which corresponds to the IUPAC definition of oxidation state. Measure of LI U in U@C 27 B also confirms the U(VI) oxidation state.…”

[Sc©[3]CPP]+: A Viable Metal-Centered [3]Cycloparaphenylene

“…To verify the formal charge state of center metal atoms, we calculated the localization indices (LI) , for [M©[3]­CPP] complexes, and the values are 9.80, 9.90, 17.64, 17.88, and 7.69 |e| for Na, Mg, Ca, Sc, and Y in [Na©[3]­CPP] − , [Mg©[3]­CPP], [Ca©[3]­CPP], [Sc©[3]­CPP] + , and [Y©[3]­CPP] + complexes, respectively. Considering the number of electrons in neutral metals, 11, 12, 20, 21, and 11 for Na, Mg, Ca, Sc, and Y, the differences of 1.20, 2.10, 2.36, 3.12, and 3.31 |e| indicate that these metals should be Na + , Mg 2+ , Ca 2+ , Sc 3+ , and Y 3+ , respectively.…”

“…To verify the formal charge state of center metal atoms, we calculated the localization indices (LI) 54,55 for [M© [3] 3+ , and Y 3+ , respectively. Please note that when the def2-TZVPP basis set is used, 28 core electrons of Y are included in the effective core potential, so Y only has 11 electrons (39−28) in this case.…”