Alkaline earth metals: homometallic bonding

Boronski, Josef T.

doi:10.1039/d3dt03550f

Dalton Trans.

2024

DOI: 10.1039/d3dt03550f

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Alkaline earth metals: homometallic bonding

Josef T. Boronski

Abstract: A discussion of the nature of homometallic alkaline earth bonding is presented, recent synthetic advances are described, and future directions are considered.

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Cited by 8 publications

References 68 publications

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Synthesis and Characterization of Bulky 1,3‐Diamidopropane Complexes of Group 2 Metals (Be−Sr)

Nguyen,

Helling,

Jones

2024

Chemistry An Asian Journal

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Reaction of lithium 1,3‐diamidopropane Li2(TripNCN) (TripNCN = [{(Trip)NCH2}2CH2]2‐, Trip = 2,4,6‐triisopropylphenyl) with BeBr2(OEt2)2 gave the diamido beryllium complex, [(TripNCN)Be(OEt2)]. Deprotonation reactions between the bulkier 1,3‐diaminopropane (TCHPNCN)H2 (TCHPNCN = [{(TCHP)NCH2}2CH2]2‐, TCHP = 2,4,6‐tricyclohexylphenyl) and magnesium alkyls afforded the adduct complexes [(TCHPNCN)Mg(OEt2)] and [(TCHPNCN)Mg(THF)2], depending on the reaction conditions employed. Treating [(TCHPNCN)Mg(THF)2] with the N‐heterocyclic carbene:C{(MeNCMe)2} (TMC) gave [(TCHPNCN)Mg(TMC)2] via substitution of the THF ligands. Reactions of (ArNCN)H2 (Ar = Trip or TCHP) with Mg{CH2(SiMe3)}2, in the absence of Lewis bases, yielded the N‐bridged dimers [{(ArNCN)Mg}2]. Salt metathesis reactions between alkali metal salts M2(TCHPNCN) (M = Li or K) and CaI2 or SrI2 led to the THF adduct compounds [(TCHPNCN)Ca(THF)3] and [(TCHPNCN)Sr(THF)4], the differing number of THF ligands in which are a result of the different sizes of the metals involved. The described complexes hold potential as precursors to kinetically protected, low oxidation state group 2 metal species.

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Synthesis and Characterization of Bulky 1,3‐Diamidopropane Complexes of Group 2 Metals (Be−Sr)

Nguyen,

Helling,

Jones

2024

Chemistry An Asian Journal

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Prediction of Covalent Metal‐Metal Bonding in Cp−M−M’‐Nacnac Complexes of Group 2 and 12 Metals (Be, Mg, Ca, Zn, Cd, Hg)

Gosch,

Wilson

2024

Chemistry A European J

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Bimetallic CpMM'Nacnac molecules with group 2 and 12 metals (M = Be, Mg, Ca, Zn, Cd, Hg) that contain novel metal‐metal bonding have been investigated in a theoretical study of their molecular and electronic structure, thermodynamic stability, and metal‐metal bonding. In all cases the metal‐metal bonds are characterized as electron‐sharing covalent single bonds from natural bond orbital (NBO) and energy‐decomposition analysis with natural orbitals of chemical valence (EDA‐NOCV) analysis. The sum of [MM'] charges is relatively constant, with all complexes exhibiting a [MM']2+ core. Quantum theory of atoms in molecules (QTAIM) analysis indicates the presence of non‐nuclear attractors (NNA) in the metal‐metal bonds of the BeBe, MgMg, and CaCa complexes. There is substantial electron density (0.75‐1.33 e) associated with the NNAs, which indicates that these metal‐metal bonds, while classified as covalent electron‐sharing bonds, retain significant metallic character that can be associated with reducing reactivity of the complex. The predicted stability of these complexes, combined with their novel covalent metal‐metal bonding and potential as reducing agents, make them appealing targets for the synthesis of new metal‐metal bonds.

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Mechanochemical Synthesis, Characterization and Reactivity of a Room Temperature Stable Calcium Electride

Bowles,

Quirk,

Liu

et al. 2024

J. Am. Chem. Soc.

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A new calcium-based Room temperature Stable Electride (RoSE), K[{Ca[N(Mes)(SiMe 3 )] 3 (e − )} 2 K 3 ] (2), is successfully synthesized from the reaction of a calcium tris-amide, [Ca{N(Mes)(SiMe 3 )} 3 K] (1) (Mes = 2,4,6-trimethylphenyl), with potassium under mechanochemical treatment. The dimeric structure of K[{Ca[N(Mes)(SiMe 3 )] 3 (e − )} 2 K 3 ] is calculated using ab initio random structure searching (AIRSS) methods. This shows the existence of highly localized anionic electrons (e − ) and suggests poor electrical conductance, as confirmed via electroconductivity measurements. The two anionic electrons in 2 are strongly antiferromagnetically coupled, thus in agreement with the largely diamagnetic response from magnetometry. Reaction of 2 with pyridine affords 4,4′bipyridine, while reaction with benzene gives C−H activation and formation of a calcium hydride complex, [K(η 6 -C 6 H 6 ) 4 ][{Ca[N(Mes)(SiMe 3 )](H)} 2 K 3 ] (3). Computational DFT analysis reveals the crucial role played by the ligand framework in the stabilization of this new Ca-hydride complex.

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Alkaline earth metals: homometallic bonding

Abstract: A discussion of the nature of homometallic alkaline earth bonding is presented, recent synthetic advances are described, and future directions are considered.

Cited by 8 publications

References 68 publications

Synthesis and Characterization of Bulky 1,3‐Diamidopropane Complexes of Group 2 Metals (Be−Sr)

Synthesis and Characterization of Bulky 1,3‐Diamidopropane Complexes of Group 2 Metals (Be−Sr)

Prediction of Covalent Metal‐Metal Bonding in Cp−M−M’‐Nacnac Complexes of Group 2 and 12 Metals (Be, Mg, Ca, Zn, Cd, Hg)

Mechanochemical Synthesis, Characterization and Reactivity of a Room Temperature Stable Calcium Electride

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