Switchable dual bonding nature in silabicyclo[1.1.0]butanes that exhibit bond stretch isomerism

Chinaroj, Siwat; Iwamoto, Takeaki

doi:10.1002/poc.4019

Cited by 5 publications

(8 citation statements)

References 55 publications

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“…Ther ecent activity is indicative that the CSB concept is already stimulating chemists,t hrough articulations of the concept by experimental chemists, [78,81,82] and through QTAIM and ELF analyses of experimental electron densities, isodesmic reaction tests, [52,54,55,58,59,[87][88][89][90] and explorations of how protonation of heteroatoms change their bonds to CSBs, [91] inverted Si-Si CSBs in silabicyclo[1.1.0]butanes, [92] and predictions of novel helium bonds, [57] which reveal CSB characteristics.S ince the chemical bond is the heartland of chemistry, [1] we might expect this trend to continue.…”

Section: Articulation Of the Potential Catalytic Role Of Charge-shiftmentioning

confidence: 99%

Charge‐Shift Bonding: A New and Unique Form of Bonding

et al. 2019

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Charge‐shift bonds (CSBs) constitute a new class of bonds different than covalent/polar‐covalent and ionic bonds. Bonding in CSBs does not arise from either the covalent or the ionic structures of the bond, but rather from the resonance interaction between the structures. This Essay describes the reasons why the CSB family was overlooked by valence‐bond pioneers and then demonstrates that the unique status of CSBs is not theory‐dependent. Thus, valence bond (VB), molecular orbital (MO), and energy decomposition analysis (EDA), as well as a variety of electron density theories all show the distinction of CSBs vis‐à‐vis covalent and ionic bonds. Furthermore, the covalent–ionic resonance energy can be quantified from experiment, and hence has the same essential status as resonance energies of organic molecules, e.g., benzene. The Essay ends by arguing that CSBs are a distinct family of bonding, with a potential to bring about a Renaissance in the mental map of the chemical bond, and to contribute to productive chemical diversity.

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Section: Articulation Of the Potential Catalytic Role Of Charge-shiftmentioning

confidence: 99%

Charge‐Shift Bonding: A New and Unique Form of Bonding

et al. 2019

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“…The recent activity is indicative that the CSB concept is already stimulating chemists, through articulations of the concept by experimental chemists, and through QTAIM and ELF analyses of experimental electron densities, isodesmic reaction tests, and explorations of how protonation of heteroatoms change their bonds to CSBs, inverted Si–Si CSBs in silabicyclo[1.1.0]butanes, and predictions of novel helium bonds, which reveal CSB characteristics. Since the chemical bond is the heartland of chemistry, we might expect this trend to continue.…”

Section: How Do We Define a New Class Of Bonding?mentioning

confidence: 99%

Charge‐Shift Bonding: A New and Unique Form of Bonding

et al. 2019

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Stichwçrter: bond theory ·charge-shift bonds · covalent bonds ·ionic bonds ·v alence bonds Dedicated to Roald HoffmannAbstract: Charge-shift bonds (CSBs) constitute anew class of bonds different than covalent/polar-covalent and ionic bonds. Bonding in CSBs does not arise from either the covalent or the ionic structures of the bond, but rather from the resonance interaction between the structures.T his Essay describes the reasons why the CSB family was overlooked by valence-bond pioneers and then demonstrates that the unique status of CSBs is not theory-dependent. Thus,v alence bond (VB), molecular orbital (MO), and energy decomposition analysis (EDA), as well as av ariety of electron density theories all show the distinction of CSBs vis-à-vis covalent and ionic bonds. Furthermore,t he covalent-ionic resonance energy can be quantified from experiment, and hence has the same essential status as resonance energies of organic molecules,e .g., benzene. The Essaye nds by arguing that CSBs are ad istinct family of bonding,w ith ap otential to bring about aR enaissance in the mental map of the chemical bond, and to contribute to productive chemical diversity.

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“…The dominant size of RE CS generally evolves in order to lower the kinetic-energy imbalance in systems having extreme Pauli repulsion pressure in the bonding region. , The Pauli repulsion eventually weakens the covalent component of the bond, and in some cases, makes the corresponding wave function even repulsive, and confers bond lengthening as in the F–F bond, wherein the σ-lone pairs impair the covalent bonding . The CS family has now been expanded to a variety of main-group compounds like the bond between halogens, oxygen–oxygen single bonds, the bridge-bond in [1.1.1]propellane and silabicyclo[1.1.0]butanes, dative bonds, bonds in hypervalent compounds, the C–N and C–O bonds in protonated amines and alcohols, and so on …”

Section: Introductionmentioning

confidence: 99%

Covalent vs Charge-Shift Nature of the Metal–Metal Bond in Transition Metal Complexes: A Unified Understanding

2020

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We present here a general conceptualization of the nature of metal–metal (M–M) bonding in transition-metal (TM) complexes across the periods of TM elements, by use of ab initio valence-bond theory. The calculations reveal a dual-trend: For M–M bonds in groups 7 and 9, the 3d-series forms charge-shift bonds (CSB), while upon moving down to the 5d-series, the bonds become gradually covalent. In contrast, M–M bonds of metals having filled d-orbitals (groups 11 and 12) behave oppositely; initially the M-M bond is covalent, but upon moving down the Periodic Table, the CSB character increases. These trends originate in the radial-distribution-functions of the atomic orbitals, which determine the compactness of the valence-orbitals vis-à-vis the filled semicore orbitals. Key factors that gauge this compactness are the presence/absence of a radial-node in the valence-orbital and relativistic contraction/expansion of the valence/semicore orbitals. Whenever these orbital-types are spatially coincident, the covalent bond-pairing is weakened by Pauli-repulsion with the semicore electrons, and CSB takes over. Thus, for groups 3–10, which possess (n – 1)s2(n – 1)p6 semicores, this spatial-coincidence is maximal at the 3d-transition-metals which consequently form charge-shift M–M bonds. However, in groups 11 and 12, the relativistic effects maximize spatial-coincidence in the third series, wherein the 5d10 core approaches the valence 6s orbital, and the respective Pauli repulsion generates M–M bonds with CSB character. These considerations create a generalized paradigm for M–M bonding in the transition-elements periods, and Pauli repulsion emerges as the factor that unifies CSB over the periods of main-group and transition elements.

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Switchable dual bonding nature in silabicyclo[1.1.0]butanes that exhibit bond stretch isomerism

Cited by 5 publications

References 55 publications

Charge‐Shift Bonding: A New and Unique Form of Bonding

Charge‐Shift Bonding: A New and Unique Form of Bonding

Charge‐Shift Bonding: A New and Unique Form of Bonding

Covalent vs Charge-Shift Nature of the Metal–Metal Bond in Transition Metal Complexes: A Unified Understanding

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