The directional bonding of [1.1.1]propellane with next generation QTAIM

Xin, Bin; Xu, Ting; Kirk, Steven R.; Jenkins, Samantha

doi:10.1016/j.cplett.2019.06.054

Cited by 18 publications

(42 citation statements)

References 29 publications

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“…Thea uthors concluded that the inverted CÀCb ond is aCSB with significant "metallicity" and polarizability. [26] This conclusion is in line with the respective computed Laplacians (Lap =+0.1! + 0.14 vs. À0.40!À0.47, respectively [26] )a nd those quantified from experimental electron density, [52] for the inverted vs.wing CÀCb onds.…”

Section: Electronic-stress Tensor (Est) Analysis Of the Density In Cosupporting

confidence: 82%

“…[52] TheL aplacians have different signs and demonstrate that the wing CÀCbonds are covalent bonds, while the inverted central CÀCb ond is aC SB.T hese assignments are in full accord with the conclusions of ab initio VB calculations [37] as well as MP2-and CCSDcalculated values in Scheme 2. [26] Ther ecent study of the O À Obond in the crystal structure of Rubrene endo-peroxide shows an agreement between experiment and theory that the bond is aCSB.Asimilar finding pertains to the MnÀMn bond in Mn 2 (CO) 10 ,w hich is CSB [23] and its experimental and theoretical Laplacian values are positive. [55] Thus,e lectron density determined by either experiment or theoretical calculations leads to ap ositive Laplacian, and to other criteria that suit CSBs.…”

Section: Comparison Of Laplacian Values To Experimental Datamentioning

confidence: 73%

“…Then ature of bonds can also be classified based on the mechanical properties of the electron density that are derived from the electronic-stress tensor. [25,26,68,69] Them echanical information is associated with three eigenvalues (l 1 -l 3 )ofthis density-tensor at the bond critical point (r c ). Thetensile mode, tangent to the bond axis,p ossesses an eigenvalue (l 3 ), which indicates the extent whereby the electron density is attracted to the nuclei, while the compressive modes,perpendicular to the bond axis,p ossess eigenvalues (l 1 and l 2 )t hat indicate how much the electrons are attracted to the center of the bonding region.…”

Section: Electronic-stress Tensor (Est) Analysis Of the Density In Comentioning

confidence: 99%

“…Thel atter values vary in the same manner as above,a nd are small (< 1) for covalent bonds and large for CSBs:0 .69 (for CÀC) vs.2 .0 (for OÀO) and 2.7 (for FÀF), again in the order of the respective RE CS for these bonds. [25] More recently,Jenkins et al [26] calculated the L rel property for the inverted bond of [1.1.1]propellane at different levels. As shown in Scheme 2, the values for the inverted bond, 3.4-3.8, are much larger than those for the covalent wing bonds (< 1).…”

Section: Electronic-stress Tensor (Est) Analysis Of the Density In Comentioning

confidence: 99%

“…As this Essay demonstrates,b ecause ab initio VB calculations were not available when Pauling developed his bonding ideas,heused approximations.One of these approximations resulted in the complete lack of recognition of af amily of bonds:t he charge-shift bond (CSB) family.A s such, this Essay deals with this new bonding form that is supported by both VB-and MO-based theories, [21,22] as well as by ar ecent energy decomposition analysis (EDA) scheme devised by Head-Gordon et al [23] CSB is further categorized independently by electron density theories (QTAIM, [24] electron density tensor theory, [25,26] and ELF [27,28] ), and supported by experimental data. TheC SB family is wideranging,i nvolving homonuclear and heteronuclear bonds,o f s and p types,aswell as dative,coordinative,and hypervalent bonds.…”

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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: Electronic-stress Tensor (Est) Analysis Of the Density In Cosupporting

confidence: 82%

Section: Comparison Of Laplacian Values To Experimental Datamentioning

confidence: 73%

Section: Electronic-stress Tensor (Est) Analysis Of the Density In Comentioning

confidence: 99%

Section: Electronic-stress Tensor (Est) Analysis Of the Density In Comentioning

confidence: 99%

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

et al. 2019

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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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Comment on “The ‘Inverted Bonds’ Revisited. Analysis of ‘in Silico’ Models and of [1.1.1]Propellane Using Orbital Forces“

Braı̈da

Shaik

et al. 2020

Chemistry A European J

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In ar ecent publication in this journal, Laplaza, Contreras-Garcia, Fuster,V olatron and Chaquin [1] (LCFVC) report an application of the Dynamical Orbital Forces (DOF) method, [2] which was used by the authorst oc hallenge the presence of an inverted central CÀCb ond in [1.1.1]propellane (1 in Scheme 1), which was suggested to exist long ago by Jackson and Allen, [3] then by Feller and Davidson, [4] and recently given theoretical support on the basis of ab initio valence bond calculations. [5] The DOF of am olecular orbital (MO) is the derivativeo fi ts energy with respectt od istanceb etween two atoms of the molecule. This quantity is interpreted, on the basis of Koopmans' theorem, as the force exerted on the nuclei along this interatomic distanceb yr emoval of one electron from the MO, in the frozen MO approximation.T he positive/negative sign of the DOF is used as am ean to characterize the bonding/antibondingn ature of the MO with respectt ot he two atoms in question.A sa ne xtension of this model, the DOFs with respect to ag iven interatomic distance are summed over all the MOs (f i )o fam olecule, and the result S(DOF i )i sc onsidered as the central quantity that determines the nature and strength of a particularb ond. Al arge positive S(DOF i )c orrespondst oastrong bond, [1,6,7] while an egative S(DOF i )s ignifies ar epulsive interaction. Thism ethodw as recently applied to as eries of hydrocarbons and alinear correlation was found between the CC bonding energies and the CC S(DOF i ). [7] Back to [1.1.1]propellane 1 in Scheme 1, this cage molecule was long supposed to possess as ignificant s-bond between the two bridgehead carbons [3,4] owing to its remarkably weak enthalpyo ff ormation (only 143 kcal mol À1 )b ye xtrusion of two hydrogena toms from bicyclo[1.1.1]pentane 2.T his value is significantly smaller than twice the standard bonding energy of a CÀHb ond. The presence of this central s-bond in 1 was confirmedb ya bi nitio calculations of the "breathing-orbital valence bond" (BOVB)t ype. [5] These calculations confirmed the order of magnitude of stability of ca. 60 kcal mol À1 ,that was estimated in previouss tudies for this bond based on the above thermodynamic considerations.Twof eatures of the bridgehead bond in 1 are noteworthy: 1) the bonding interaction takes place between two sp 3 -like hybrida tomico rbitals (HAOs) pointing away from the center of the molecule, hence its description as an "inverted bond"; 2) at variancew ith classical covalentb onds, the bonding strength of the bridgehead CC bond is mostly due to the stabilizing resonance interaction, C·-·C$[C + :C À + C: À C + ], that is, the resonancee nergya rising from mixingo ft he purely covalent component of the bond with its ionic components.A tt he same time, the covalent part alone C·-·C, involving singlet-coupling betweent he two electrons in the two HAOs,a lthough being significantly stabilizing, cannot by itself overcome the large repulsions from the surroundingw ing CÀCb onds, and is thus overall only slightly repulsive. Suc...

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The directional bonding of [1.1.1]propellane with next generation QTAIM

Cited by 18 publications

References 29 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

Comment on “The ‘Inverted Bonds’ Revisited. Analysis of ‘in Silico’ Models and of [1.1.1]Propellane Using Orbital Forces“

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