The Valence Orbitals of the Alkaline-Earth Atoms

Overview

Journal Chemistry

Specialty Chemistry

Date 2020 Jul 16

PMID 32666598

Citations 13

Authors

Israel Fernandez

Nicole Holzmann

Gernot Frenking

Affiliations

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Abstract

Quantum chemical calculations of the alkaline-earth oxides, imides and dihydrides of the alkaline-earth atoms (Ae=Be, Mg, Ca, Sr, Ba) and the calcium cluster Ca H [N(SiMe ) ] (pmdta) (pmdta=N,N,N',N'',N''-pentamethyldiethylenetriamine) have been carried out by using density functional theory. Analysis of the electronic structures by charge and energy partitioning methods suggests that the valence orbitals of the lighter atoms Be and Mg are the (n)s and (n)p orbitals. In contrast, the valence orbitals of the heavier atoms Ca, Sr and Ba comprise the (n)s and (n-1)d orbitals. The alkaline-earth metals Be and Mg build covalent bonds like typical main-group elements, whereas Ca, Sr and Ba covalently bind like transition metals. The results not only shed new light on the covalent bonds of the heavier alkaline-earth metals, but are also very important for understanding and designing experimental studies.

Citing Articles

Unusual quadruple bonds featuring collective interaction-type σ bonds between first octal-row atoms in the alkaline-earth compounds AeOLi (Ae = Be-Ba).

Cui L, Liu Y, Pan S, Cui Z, Frenking G Chem Sci. 2024; .

PMID: 39176245 PMC: 11337084. DOI: 10.1039/d4sc01979b.

A Lead-μ-Tetrylide Complex with Osmium(IV) Terminal Components.

Cabeza J, Esteruelas M, Fernandez I, Izquierdo S, Onate E Inorg Chem. 2024; 63(34):15563-15567.

PMID: 39102521 PMC: 11733942. DOI: 10.1021/acs.inorgchem.4c02520.

A Blueprint for the Stabilization of Sub-Valent Alkaline Earth Complexes.

Bowles A, Liu Y, Stevens M, Vitorica-Yrezabal I, McMullin C, Ortu F Chemistry. 2023; 29(54):e202301850.

PMID: 37338225 PMC: 10947258. DOI: 10.1002/chem.202301850.

Genuine quadruple bonds between two main-group atoms. Chemical bonding in AeF (Ae = Be-Ba) and isoelectronic EF (E = B-Tl) and the particular role of d orbitals in covalent interactions of heavier alkaline-earth atoms.

Liu R, Qin L, Zhang Z, Zhao L, Sagan F, Mitoraj M Chem Sci. 2023; 14(18):4872-4887.

PMID: 37181783 PMC: 10171194. DOI: 10.1039/d3sc00830d.

Origin of the Ligand Ring-Size Effect on the Catalytic Activity of Cationic Calcium Hydride Dimers in the Hydrogenation of Unactivated 1-Alkenes.

Zhu H, Qu Z, Grimme S ChemistryOpen. 2022; 11(12):e202200240.

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References

van Lenthe E, Baerends E . Optimized Slater-type basis sets for the elements 1-118. J Comput Chem. 2003; 24(9):1142-56. DOI: 10.1002/jcc.10255. View

Saha R, Pan S, Merino G, Chattaraj P . Unprecedented Bonding Situation in Viable E (NHB ) (E=Be, Mg; NHB =(HCN ) B) Complexes: Neutral E Forms a Single E-E Covalent Bond. Angew Chem Int Ed Engl. 2019; 58(25):8372-8377. DOI: 10.1002/anie.201900992. View

de Bruin-Dickason C, Sutcliffe T, Alvarez Lamsfus C, Deacon G, Maron L, Jones C . Kinetic stabilisation of a molecular strontium hydride complex using an extremely bulky amidinate ligand. Chem Commun (Camb). 2018; 54(7):786-789. DOI: 10.1039/c7cc09362d. View

Yu H, Truhlar D . What Dominates the Error in the CaO Diatomic Bond Energy Predicted by Various Approximate Exchange-Correlation Functionals?. J Chem Theory Comput. 2015; 10(6):2291-305. DOI: 10.1021/ct5000814. View

Hermann M, Frenking G . Carbones as Ligands in Novel Main-Group Compounds E[C(NHC) ] (E=Be, B , C , N , Mg, Al , Si , P ): A Theoretical Study. Chemistry. 2016; 23(14):3347-3356. DOI: 10.1002/chem.201604801. View

Zhao L, Pan S, Holzmann N, Schwerdtfeger P, Frenking G . Chemical Bonding and Bonding Models of Main-Group Compounds. Chem Rev. 2019; 119(14):8781-8845. DOI: 10.1021/acs.chemrev.8b00722. View

Stegner P, Farber C, Oetzel J, Siemeling U, Wiesinger M, Langer J . d-d Dative Bonding Between Iron and the Alkaline-Earth Metals Calcium, Strontium, and Barium. Angew Chem Int Ed Engl. 2020; 59(34):14615-14620. PMC: 7496664. DOI: 10.1002/anie.202005774. View

Couchman S, Holzmann N, Frenking G, Wilson D, Dutton J . Beryllium chemistry the safe way: a theoretical evaluation of low oxidation state beryllium compounds. Dalton Trans. 2013; 42(32):11375-84. DOI: 10.1039/c3dt50563d. View

Chi C, Pan S, Meng L, Luo M, Zhao L, Zhou M . Alkali Metal Covalent Bonding in Nickel Carbonyl Complexes ENi(CO). Angew Chem Int Ed Engl. 2018; 58(6):1732-1738. DOI: 10.1002/anie.201813022. View

10.

Frenking G, Frohlich N . The nature of the bonding in transition-metal compounds. Chem Rev. 2001; 100(2):717-74. DOI: 10.1021/cr980401l. View

11.

Jones C, Bonyhady S, Holzmann N, Frenking G, Stasch A . Preparation, characterization, and theoretical analysis of group 14 element(I) dimers: a case study of magnesium(I) compounds as reducing agents in inorganic synthesis. Inorg Chem. 2011; 50(24):12315-25. DOI: 10.1021/ic200682p. View

12.

Green S, Jones C, Stasch A . Stable magnesium(I) compounds with Mg-Mg bonds. Science. 2007; 318(5857):1754-7. DOI: 10.1126/science.1150856. View

13.

Jerabek P, Schwerdtfeger P, Frenking G . Dative and electron-sharing bonding in transition metal compounds. J Comput Chem. 2018; 40(1):247-264. DOI: 10.1002/jcc.25584. View

14.

Glendening E, Landis C, Weinhold F . NBO 6.0: natural bond orbital analysis program. J Comput Chem. 2013; 34(16):1429-37. DOI: 10.1002/jcc.23266. View

15.

Dutton J, Frenking G . New Avenues in s-Block Chemistry: Beryllium(0) Complexes. Angew Chem Int Ed Engl. 2016; 55(43):13380-13382. DOI: 10.1002/anie.201606244. View

16.

Koch D, Chen Y, Golub P, Manzhos S . Revisiting π backbonding: the influence of d orbitals on metal-CO bonds and ligand red shifts. Phys Chem Chem Phys. 2019; 21(37):20814-20821. DOI: 10.1039/c9cp04624k. View

17.

Michalak A, Mitoraj M, Ziegler T . Bond orbitals from chemical valence theory. J Phys Chem A. 2008; 112(9):1933-9. DOI: 10.1021/jp075460u. View

18.

Fernandez I, Holzmann N, Frenking G . The Valence Orbitals of the Alkaline-Earth Atoms. Chemistry. 2020; 26(62):14194-14210. PMC: 7702052. DOI: 10.1002/chem.202002986. View

19.

Landis C, Hughes R, Weinhold F . Comment on "Observation of alkaline earth complexes M(CO) (M = Ca, Sr, or Ba) that mimic transition metals". Science. 2019; 365(6453). DOI: 10.1126/science.aay2355. View

20.

Bauer H, Alonso M, Fischer C, Rosch B, Elsen H, Harder S . Simple Alkaline-Earth Metal Catalysts for Effective Alkene Hydrogenation. Angew Chem Int Ed Engl. 2018; 57(46):15177-15182. DOI: 10.1002/anie.201810026. View