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Alkaline earth metals: homometallic bonding

DALTON TRANSACTIONS (2023)

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Article Chemistry, Multidisciplinary

Synthesis and Crystallographic Characterization of a Reduced Bimetallic Yttrium ansa-Metallocene Hydride Complex, [K(crypt)][(μ- CpAn)Y(μ-H)]2 (CpAn=Me2Si[C5H3(SiMe3)-3]2), with a 3.4 Å Yttrium-Yttrium Distance

Justin C. Wedal et al.

Summary: The reduction of a bimetallic yttrium ansa-metallocene hydride was studied, and the formation of Y-Y bonds was explored. The precursor [CpAnY(mu-H)(THF)]2 was synthesized by hydrogenolysis of the allyl complex CpAnY(I3-C3H5)(THF), which was prepared from (C3H5)MgCl and [CpAnY(mu-Cl)]2. Treatment of [CpAnY(mu-H)(THF)]2 with excess KC8 in the presence of 2.2.2-cryptand (crypt) resulted in the formation of [K(crypt)][(mu-CpAn)Y(mu-H)]2. The reduced anion [(mu-CpAn)Y(mu-H)]21- showed the shortest Y···Y distances observed to date and exhibited Y(II) characteristics.

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY (2023)

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Article Chemistry, Multidisciplinary

Inducing Nucleophilic Reactivity at Beryllium with an Aluminyl Ligand

Josef T. Boronski et al.

Summary: The reaction of beryllocene with anionic aluminium or gallium nucleophiles resulted in the formation of compounds with Be-Al or Be-Ga bonds. The beryllium-aluminyl complex exhibited a shorter Be-Al bond length and the existence of a non-nuclear attractor for the Be-Al interaction. The calculated charge distribution suggested nucleophilic behavior at beryllium which correlated with the observed reactivity.

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY (2023)

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Article Multidisciplinary Sciences

Diberyllocene, a stable compound of Be(I) with a Be-Be bond

Josef T. Boronski et al.

Summary: The complex diberyllocene CpBeBeCp has been studied for five decades but its experimental characterization has not been achieved until now. We have successfully prepared and isolated this compound by reducing beryllocene with a dimeric magnesium(I) complex, and its structure in the solid state was determined using x-ray crystallography. Diberyllocene acts as a reductant in reactions that form beryllium-aluminum and beryllium-zinc bonds. Quantum chemical calculations suggest similarities between the electronic structure of diberyllocene and the simple homodiatomic species diberyllium (Be2).

SCIENCE (2023)

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Article Chemistry, Multidisciplinary

Reduction of Na+ within a {Mg2Na2} Assembly

Han-Ying Liu et al.

Summary: Ionic compounds containing sodium cations are known for their stability and resistance to redox reactivity. However, when treated with non-reducible organic bases, a low oxidation state {Mg2Na2} species undergoes selective extrusion of sodium metal and oxidation of the Mg-I centers. Quantum chemical studies indicate that intramolecular electron transfer is facilitated by the molecular orbitals of the {Mg2Na2} ensemble.

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION (2023)

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Article Chemistry, Inorganic & Nuclear

Heteronuclear and Homonuclear Bimetallic Metallocenes of Alkaline Earths and Zinc

Matthew A. Gosch et al.

ORGANOMETALLICS (2023)

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Article Chemistry, Multidisciplinary

Coordination and Activation of N-2 at Low-Valent Magnesium using a Heterobimetallic Approach: Synthesis and Reactivity of a Masked Dimagnesium Diradical

Rahul Mondal et al.

Summary: The reduction of a bulky magnesium(II) amide with 5% w/w K/KI yields a magnesium-N-2 complex, which can reductively activate CO, H-2 and C2H4, acting as a masked dimagnesium(I) diradical.

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION (2023)

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Article Chemistry, Multidisciplinary

Access to a Labile Monomeric Magnesium Radical by Ball-Milling

Dawid Jedrzkiewicz et al.

Summary: This research focuses on the study of magnesium radicals and successfully isolates a monometallic magnesium radical. The crystal structure of the low-valent magnesium-iodine complex reveals strong bonding between magnesium and the ligand. Calculations show similar metal-to-CAAC charge transfer in different complexes.

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION (2022)

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Article Chemistry, Inorganic & Nuclear

Low-valent Mg(I) complexes by ball-milling

Dawid Jedrzkiewicz et al.

Summary: Mechanochemistry shows great potential in synthesizing low-valent Mg(I) complexes. Reduction of magnesium iodide precursors with different beta-diketiminate (BDI) ligands using ball-milling resulted in colored powders containing (BDI)Mg center dot radicals. Extraction with different solvents yielded various complex compounds.

ZEITSCHRIFT FUR ANORGANISCHE UND ALLGEMEINE CHEMIE (2022)

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Article Chemistry, Multidisciplinary

Photochemically Activated Dimagnesium(I) Compounds: Reagents for the Reduction and Selective C-H Bond Activation of Inert Arenes

Dafydd D. L. Jones et al.

Summary: The study reported the photochemical activation of dimagnesium(I) compounds with inert arenes, leading to high yielding, regioselective reactions. Computational studies suggested that all reactions proceed via photochemically generated magnesium(I) radicals, which reduce the arene substrate before C-H or C-F bond activation processes occur.

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION (2021)

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Article Chemistry, Multidisciplinary

Reductive Dimerization of CO by a Na/Mg(I) Diamide

Han-Ying Liu et al.

Summary: Sodium reduction of [{SiNDipp}Mg] leads to the formation of [{SiNDipp}MgNa](2), which features a long Mg-Mg bond enhanced by persistent Na-aryl interactions. The computational assessment suggests that this molecule should be considered as a contiguous tetrametallic core, supported by its reaction with CO to form ethynediolate mediated by dissimilar metal centers.

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY (2021)

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Article Multidisciplinary Sciences

Dinitrogen complexation and reduction at low-valent calcium

B. Roesch et al.

Summary: The attempted preparation of low-valent Ca-I complexes in the form of LCa-CaL under dinitrogen atmosphere led to the isolation of LCa(N-2)CaL, which acts as a synthon for the target LCa-CaL.The N-2(2-) anion in this complex reacted as a potent two-electron donor and could be protonated to diazene. The role of Ca d orbitals in N-2 activation is also discussed.

SCIENCE (2021)

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Article Multidisciplinary Sciences

Strongly reducing magnesium(0) complexes

B. Roesch et al.

Summary: This article reports on beta-diketiminate complexes containing magnesium in its zero oxidation state, showcasing the reactivity and stability of such compounds. These complexes are discussed as potential reducing agents with electron-rich Mg centers.

NATURE (2021)

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Review Chemistry, Multidisciplinary

Transition-Metal Chemistry of the Heavier Alkaline Earth Atoms Ca, Sr, and Ba

Mingfei Zhou et al.

Summary: The alkaline earth elements, previously considered chemically uninteresting, are now recognized for their rich covalent chemistry and similar coordination structures to classic transition metals. Their properties and structures suggest a classification closer to transition metals rather than main group elements.

ACCOUNTS OF CHEMICAL RESEARCH (2021)

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Article Multidisciplinary Sciences

A crystalline tri-thorium cluster with σ-aromatic metal-metal bonding

Josef T. Boronski et al.

Summary: Actinide-actinide bonding is typically predicted to be weak and difficult to observe under normal conditions, but the experimental discovery of thorium-thorium bonding in a crystalline cluster has revealed a new type of sigma-aromatic bond that challenges previous theoretical predictions. This discovery extends delocalized sigma-aromatic bonding to the heaviest elements in the periodic table and offers a new approach to studying actinide-actinide bonding.

NATURE (2021)

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Article Chemistry, Multidisciplinary

New horizons in low oxidation state group 2 metal chemistry

Bastian Roesch et al.

Summary: Research on low-valent complexes of magnesium has made significant progress, from breaking the Mg-I-Mg-I bond to reducing aromatic solvents, to isolating zero-valent complexes and fixing molecular nitrogen. These studies have sparked great interest and potential for new reactivities and applications in the field of group 2 metal chemistry.

CHEMICAL COMMUNICATIONS (2021)

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A Stable, Crystalline Beryllium Radical Cation

Guocang Wang et al.

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY (2020)

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Formation of the End-on Bound Lanthanide Dinitrogen Complexes [(R2N)3Ln-N=N-Ln(NR2)3]2- from Divalent [(R2N)3Ln]1- Salts (R = SiMe3)

Austin J. Ryan et al.

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY (2020)

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The Valence Orbitals of the Alkaline-Earth Atoms

Israel Fernandez et al.

CHEMISTRY-A EUROPEAN JOURNAL (2020)

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Open questions in low oxidation state group 2 chemistry

Cameron Jones

COMMUNICATIONS CHEMISTRY (2020)

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Review Chemistry, Multidisciplinary

Beryllium coordination chemistry and its implications on the understanding of metal induced immune responses

Magnus R. Buchner

CHEMICAL COMMUNICATIONS (2020)

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Article Chemistry, Multidisciplinary

Soft interactions with hard Lewis acids: generation of mono- and dicationic alkaline-earth metal arene-complexes by direct oxidation

Marcel Schorpp et al.

CHEMICAL SCIENCE (2020)

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Article Chemistry, Multidisciplinary

Reductive Trimerization of CO to the Deltate Dianion Using Activated Magnesium(I) Compounds

K. Yuvaraj et al.

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY (2019)

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Review Chemistry, Multidisciplinary

Recent Contributions to the Coordination Chemistry of Beryllium

Magnus R. Buchner

CHEMISTRY-A EUROPEAN JOURNAL (2019)

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Article Chemistry, Multidisciplinary

Low Valent Magnesium Chemistry with a Super Bulky β-Diketiminate Ligand

Thomas Xaver Gentner et al.

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION (2019)

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Barium as Honorary Transition Metal in Action: Experimental and Theoretical Study of Ba(CO)(+) and Ba(CO)(-)

Xuan Wu et al.

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION (2018)

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Article Chemistry, Inorganic & Nuclear

Multigram Syntheses of Magnesium(I) Compounds Using Alkali Metal Halide Supported Alkali Metals as Dispersible Reducing Agents

Jamie Hicks et al.

ORGANOMETALLICS (2018)

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Review Chemistry, Multidisciplinary

Dimeric magnesium(I) β-diketiminates: a new class of quasi-universal reducing agent

Cameron Jones

NATURE REVIEWS CHEMISTRY (2017)

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Off the Beaten TrackA Hitchhiker's Guide to Beryllium Chemistry

Dominik Naglav et al.

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION (2016)

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Alkaline earths as main group reagents in molecular catalysis

Michael S. Hill et al.

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U. Dammalapati et al.

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Beryllium chemistry the safe way: a theoretical evaluation of low oxidation state beryllium compounds

Shannon A. Couchman et al.

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Metal-Metal and Metal-Ligand Bonds in (η5-C5H5)2M2 (M = Be, Mg, Ca, Ni, Cu, Zn)

Xiaoyan Li et al.

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Hunting for the Magnesium(I) Species: Formation, Structure, and Reactivity of some Donor-Free Grignard Compounds

Tomasz Kruczynski et al.

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION (2012)

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Three-Coordinate Beryllium β-Diketiminates: Synthesis and Reduction Chemistry

Merle Arrowsmith et al.

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Corrected Values for Boiling Points and Enthalpies of Vaporization of Elements in Handbooks

Yiming Zhang et al.

JOURNAL OF CHEMICAL AND ENGINEERING DATA (2011)

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First Experimental Characterization of a Non-nuclear Attractor in a Dimeric Magnesium(I) Compound

James A. Platts et al.

JOURNAL OF PHYSICAL CHEMISTRY A (2011)

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Binuclear Alkaline Earth Metal Compounds (Be, Mg, Ca, Sr, Ba) with α-Diimine Ligands: A Computational Study

Shaoguang Li et al.

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Sjoerd Harder

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beta-Diketiminate-Stabilized Magnesium(I) Dimers and Magnesium(II) Hydride Complexes: Synthesis, Characterization, Adduct Formation, and Reactivity Studies

Simon J. Bonyhady et al.

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Experimental Electron Density Study of the Mg-Mg Bonding Character in a Magnesium(I) Dimer

Jacob Overgaard et al.

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Konrad Patkowski et al.

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Jeremy M. Merritt et al.

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Ralf Koeppe et al.

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION (2008)

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Stable Adducts of a Dimeric Magnesium(I) Compound

Shaun P. Green et al.

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Shaun P. Green et al.

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Alejandro Velazquez et al.

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