Chemistry of alkaline earth metals: It is not all ionic and definitely not boring!

Fromm, Katharina M.

doi:10.1016/j.ccr.2020.213193

Cited by 71 publications

(45 citation statements)

References 124 publications

(159 reference statements)

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“…Atoms from elements of groups 13-18 covalently bound to electron-withdrawing groups (EWGs) possess a strong ability to interact with Lewis bases (e.g., lone pair donors, anions, and π systems) [1][2][3][4][5][6][7][8][9][10][11][12][13]. Since the electropositive site was used to define the hydrogen bonding (HB) interaction, scientists have started to use the name of the group to which the electrophilic atom belongs to name the noncovalent interactions (NCIs) between electrophilic and nucleophilic sites [14,15].…”

Section: Introductionmentioning

confidence: 99%

On the Importance of σ–Hole Interactions in Crystal Structures

Frontera

Bauzá

2021

Crystals

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Elements from groups 14–18 and periods 3–6 commonly behave as Lewis acids, which are involved in directional noncovalent interactions (NCI) with electron-rich species (lone pair donors), π systems (aromatic rings, triple and double bonds) as well as nonnucleophilic anions (BF4−, PF6−, ClO4−, etc.). Moreover, elements of groups 15 to 17 are also able to act as Lewis bases (from one to three available lone pairs, respectively), thus presenting a dual character. These emerging NCIs where the main group element behaves as Lewis base, belong to the σ–hole family of interactions. Particularly (i) tetrel bonding for elements belonging to group 14, (ii) pnictogen bonding for group 15, (iii) chalcogen bonding for group 16, (iv) halogen bonding for group 17, and (v) noble gas bondings for group 18. In general, σ–hole interactions exhibit different features when moving along the same group (offering larger and more positive σ–holes) or the same row (presenting a different number of available σ–holes and directionality) of the periodic table. This is illustrated in this review by using several examples retrieved from the Cambridge Structural Database (CSD), especially focused on σ–hole interactions, complemented with molecular electrostatic potential surfaces of model systems.

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Section: Introductionmentioning

confidence: 99%

On the Importance of σ–Hole Interactions in Crystal Structures

Frontera

Bauzá

2021

Crystals

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“…Upon increasing the element number of a noble gas with outer closed shell 1s 2 , 2p 6 , 3p 6 , …, the additional electrons in the respective alkali and alkaline earth metals of periods n = 2, 3, 4, … are accommodated in the rather diffuse ( n sp) 2 valence shell (with the option of some ( n -1)d admixture from period n = 4 onward (Woolman et al, 2018 ; Li et al, 2019 ; Fromm, 2020 ). The s-block elements appear strictly mono- and di-valent under common conditions.…”

Section: The Blocksmentioning

confidence: 99%

“…. are accommodated in the rather diffuse (nsp) 2 valence shell (with the option of some (n-1)d admixture from period n = 4 onward (Woolman et al, 2018;Li et al, 2019;Fromm, 2020). The s-block elements appear strictly mono-and di-valent under common conditions.…”

Section: The Blocks the S-block Elementsmentioning

confidence: 99%

Understanding Periodic and Non-periodic Chemistry in Periodic Tables

et al. 2021

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The chemical elements are the “conserved principles” or “kernels” of chemistry that are retained when substances are altered. Comprehensive overviews of the chemistry of the elements and their compounds are needed in chemical science. To this end, a graphical display of the chemical properties of the elements, in the form of a Periodic Table, is the helpful tool. Such tables have been designed with the aim of either classifying real chemical substances or emphasizing formal and aesthetic concepts. Simplified, artistic, or economic tables are relevant to educational and cultural fields, while practicing chemists profit more from “chemical tables of chemical elements.” Such tables should incorporate four aspects: (i) typical valence electron configurations of bonded atoms in chemical compounds (instead of the common but chemically atypical ground states of free atoms in physical vacuum); (ii) at least three basic chemical properties (valence number, size, and energy of the valence shells), their joint variation across the elements showing principal and secondary periodicity; (iii) elements in which the (sp)8, (d)10, and (f)14valence shells become closed and inert under ambient chemical conditions, thereby determining the “fix-points” of chemical periodicity; (iv)peculiar elements at the top and at the bottom of the Periodic Table. While it is essential that Periodic Tables display important trends in element chemistry we need to keep our eyes open for unexpected chemical behavior in ambient, near ambient, or unusual conditions. The combination of experimental data and theoretical insight supports a more nuanced understanding of complex periodic trends and non-periodic phenomena.

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“…[36d,37b,57] The bonding of these oxophilic M 2 + ions with coordinating ligand is mainly governed by electrostatic and steric factors. [58] Reaction of 1 with calcium and strontium metal afforded, after crystallisation, the divalent alkaline-earth complexes [M-(IMe) 2 (THF) 2 ] (M = Ca (6), Sr ( 7)) in moderate isolated yields (48-71 %) (Scheme 1) and the complexes were characterised by IR and NMR spectroscopy. In their IR spectra, a strong absorption band is observed at ca.…”

Section: Synthesis Of Divalent Alkaline Earth Ime Complexesmentioning

confidence: 99%

Application of the Redox‐Transmetalation Procedure to Access Divalent Lanthanide and Alkaline‐Earth NHC Complexes**

Schwarz

Sun

Yadav

et al. 2021

Chemistry A European J

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Divalent lanthanide and alkaline-earth complexes supported by N-heterocyclic carbene (NHC) ligands have been accessed by redox-transmetalation between air-stable NHC-AgI complexes and the corresponding metals. By using the small ligand 1,3-dimethylimidazol-2-ylidene (IMe), two series of isostructural complexes were obtained: the tetra-NHC complexes [LnI 2 (IMe) 4 ] (Ln=Eu and Sm) and the bis-NHC complexes [MI 2 (IMe) 2 (THF) 2 ] (M=Yb, Ca and Sr). In the former, distortions in the NHC coordination were found to originate from intermolecular repulsions in the solid state. Application of the redox-transmetalation strategy with the bulkier 1,3-dimesitylimidazol-2-ylidene (IMes) ligand yielded [SrI 2 (IMes)(THF) 3 ], while using a similar procedure with Ca metal led to [CaI 2 (THF) 4 ] and uncoordinated IMes. DFT calculations were performed to rationalise the selective formation of the bis-NHC adduct in [SrI 2 (IMe) 2 (THF) 2 ] and the tetra-NHC adduct in [SmI 2 (IMe) 4 ]. Since the results in the gas phase point towards preferential formation of the tetra-NHC complexes for both metal centres, the differences between both arrangements are a result of solid-state effects such as slightly different packing forces.

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Chemistry of alkaline earth metals: It is not all ionic and definitely not boring!

Cited by 71 publications

References 124 publications

On the Importance of σ–Hole Interactions in Crystal Structures

On the Importance of σ–Hole Interactions in Crystal Structures

Understanding Periodic and Non-periodic Chemistry in Periodic Tables

Application of the Redox‐Transmetalation Procedure to Access Divalent Lanthanide and Alkaline‐Earth NHC Complexes**

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