The Valence Orbitals of the Alkaline‐Earth Atoms

Fernández, Israel; Holzmann, Nicole; Frenking, Gernot

doi:10.1002/chem.202002986

Cited by 45 publications

(56 citation statements)

References 118 publications

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“…This is another example of a polarity below the standard criterion for bond orbitals by the NBO method, which ends in a σ(Si−CO) bond. Similar situations have been recently discussed for alkaline earth oxides and imides [24] . Such a representation does not agree with the conventional understanding of the Si−CO chemical bond.…”

Section: Resultsmentioning

confidence: 54%

“…The second‐order perturbation theory predicts a high interaction that counts to 265.5 kcal/mol for 1 (Table S4). This value is too high to consider this perturbation method an accurate approach for the discussion of the interaction [24,25] …”

Section: Resultsmentioning

confidence: 97%

“…This value is too high to consider this perturbation method an accurate approach for the discussion of the interaction. [24,25] More detailed information about the nature of the SiÀ CO bonds in the silylene-carbonyl complexes and the best representation of the bonds in terms of Lewis structures are provided by the results of the Energy Decomposition Analysis (EDA) method. [22] EDA has proven to be a useful tool to assess the nature of the chemical bond in main group compounds and transition metal compounds.…”

Section: Q(simentioning

confidence: 99%

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Chemical Bonding in Silicon Carbonyl Complexes

Andrada

Sergeieva

Mandal

2021

Chemistry A European J

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Although silylene-carbonyl complexes are known for decades, only recently isolable examples have been accomplished. In this work, the bonding situation is reevaluated to explain the origins of their remarkable stability within the Kohn-Sham molecular orbital theory framework. It is shown that the chemical bond can be understood as CO interaction with the silylene via a donor-acceptor interaction: a σ-donation from the σ CO into the empty p-orbital of silicon, and a π-back donation from the sp 2 lone pair of silicon into the π* CO antibonding orbitals. Notably, it was established that the driving force behind the surprisingly stable SiÀ CO compounds, however, is another π-back donation from a perpendicular bonding RÀ Si σ-orbital into the π* CO antibonding orbitals. Consequently, the pyramidalization of the central silicon atom cannot be associated with the strength of the πback donation, in sharp contrast to the established chemical bonding model. Considering this additional bonding interaction not only shed light on the bonding situation, but is also an indispensable key for broadening the scope of silylene-carbonyl chemistry.

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Section: Resultsmentioning

confidence: 54%

Section: Resultsmentioning

confidence: 97%

Section: Q(simentioning

confidence: 99%

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Chemical Bonding in Silicon Carbonyl Complexes

Andrada

Sergeieva

Mandal

2021

Chemistry A European J

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“…One of the strengths of this method is that if there are more than one partitioning scheme available, one can choose the most suitable scheme to describe the bonding by using the size of ΔE orb as a probe. For a given interaction, those fragments, which give the lowest ΔE orb value, are the best one to describe the bonding situation as it indicates that the chosen fragments are most nearly prepared as those in the complex [69][70][71][72][73][74]. For both M(NHB Me ) 2 and M[Mn(CO) 5 ] 2 complexes, we have carried out EDA by considering M and (L) 2 with different charges and electronic states as interacting fragments.…”

Section: Resultsmentioning

confidence: 99%

Bonding in M(NHBMe)2 and M[Mn(CO)5]2 complexes (M=Zn, Cd, Hg; NHBMe=(HCNMe)2B): divalent group 12 metals with zero oxidation state

2021

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Quantum chemical studies using density functional theory were carried out on M(NHBMe)2 and M[Mn(CO)5]2 (M=Zn, Cd, Hg) complexes. The calculations suggest that M(NHBMe)2 and M[Mn(CO)5]2 have D2d and D4d symmetry, respectively, with a 1A1 electronic ground state. The bond dissociation energies of the ligands have the order of Zn > Cd > Hg. A thorough bonding analysis using charge and energy decomposition methods suggests that the title complexes are best represented as NHBMe⇆M0⇄NHBMe and Mn(CO)5⇆M0⇄Mn(CO)5 where the metal atom M in the electronic ground state with an ns2 electron configuration is bonded to the (NHBMe)2 and [Mn(CO)5]2 ligands through donor–acceptor interaction. These experimentally known complexes are the first examples of mononuclear complexes with divalent group 12 metals with zero oxidation state that are stable at ambient condition. These complexes represent the rare situation where the ligands act as a strong acceptor and the metal center acts as strong donor. The relativistic effect of Hg leads to a weaker electron donating strength of the 6s orbital, which explains the trend of the bond dissociation energy.

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“…While the ionic compounds have a formally empty valence shell, the partially covalent complexes and organometallic compounds as well as the metallic phases exhibit non-negligible s-p(d) occupation, and orbital mixing due to the small n s- n p or n s- n p-( n -1)d energy gaps. In particular, Be and Mg are n s(p) valence-active, while Ca, Sr and Ba are n s( n -1)d valence active (Fernández et al, 2020 ).…”

Section: The Blocksmentioning

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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The Valence Orbitals of the Alkaline‐Earth Atoms

Cited by 45 publications

References 118 publications

Chemical Bonding in Silicon Carbonyl Complexes

Chemical Bonding in Silicon Carbonyl Complexes

Bonding in M(NHBMe)2 and M[Mn(CO)5]2 complexes (M=Zn, Cd, Hg; NHBMe=(HCNMe)2B): divalent group 12 metals with zero oxidation state

Understanding Periodic and Non-periodic Chemistry in Periodic Tables

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