Tetracoordinate or tricoordinate? Planar tetracoordinate nitrogen in the NBe4H4- cluster stabilized by multicenter bonds.

Realization of planar tetracoordinate arrangements of nitrogen atoms is challenging because their preference for localized bonding (caused by its high electronegativity) makes them typically tricoordinate. This is especially true for the more electronegative oxygen atoms. Herein, we computationally designed two clusters NBe4H4- and OBe4H4; they contain a planar tetracoordinate nitrogen (ptN) and planar tetracoordinate oxygen (ptO) atom, respectively. Remarkably, the former is a dynamically stable global minimum, while the latter is not. The bonding analysis proves that planar tetracoordination in NBe4H4- favors over tricoordination because of the presence of multicenter delocalized bonds. In contrast, the planar tricoordination dominates due to its weak delocalized bonding ability of oxygen in the OBe4H4 cluster. Moreover, the 6σ/2π double aromaticity due to multicenter delocalized bonds allows the NBe4H4- cluster to obtain additional stability. This cluster is a promising synthetic due its dynamic and thermodynamic stability.

Comments on "Planar Tetracoordinate Hydrogen: Pushing the Limit of Multicentre Bonding".

In a recent communication (Angew. Chem. Int. Ed. 2024, 63, e202317312), Kalita et al. studied In4H+ system within the frame of single-reference approximation (SRA) and found that the global energy minimum (1 a) adopted the singlet state and a planar tetracoordinate hydrogen (ptH), while the second lowest isomer (1 b) located 3.0 kcal/mol above 1 a and adopted the triplet state as well as non-planar structure with a quasi-ptH. They assessed the reliability of SRA by checking the T1-diagnostic values of coupled cluster calculations. However, according to our multi-configurational second-order perturbation theory calculations at the CASPT2(12,13)/aug-cc-pVQZ (aug-cc-pVQZ-PP for In) level, both 1 a and 1 b exhibit obvious multi-referential characters, as reflected by their largest reference coefficients of 0.928 (86.1 %) and 0.938 (88.0 %), respectively. Moreover, 1 b is 5.05 kcal/mol lower than 1 a at this level, that is, what can be observed in In4H+ system is the quasi-ptH.

3-D molecular stars with covalent axial bonding.

In designing three-dimensional (3-D) molecular stars, it is very difficult to enhance the molecular rigidity through forming the covalent bonds between the axial and equatorial groups because corresponding axial groups will generally break the delocalized π bond over equatorial frameworks and thus break their star-like arrangement. In this work, exemplified by designing the 3-D stars Be2 ©Be5 E5 + (E = Au, Cl, Br, I) with three delocalized σ bonds and delocalized π bond over the central Be2 ©Be5 moiety, we propose that the desired covalent bonding can be achieved by forming the delocalized σ bond(s) and delocalized π bond(s) simultaneously between the axial groups and equatorial framework. The covalency and rigidity of axial bonding can be demonstrated by the total Wiberg bond indices of 1.46-1.65 for axial Be atoms and ultrashort Be-Be distances of 1.834-1.841 Å, respectively. Beneficial also from the σ and π double aromaticity, these mono-cationic 3-D molecular stars are dynamically viable global energy minima with well-defined electronic structures, as reflected by wide HOMO-LUMO gaps (4.68-5.06 eV) and low electron affinities (4.70-4.82 eV), so they are the promising targets in the gas phase generation, mass-separation, and spectroscopic characterization.

Ab Initio Metadynamics Simulations of Hexafluoroisopropanol Solvent Effects: Synergistic Role of Solvent H-Bonding Networks and Solvent-Solute C-H/π Interactions.

The solvent effects in Friedel-Crafts cycloalkylation of epoxides and Cope rearrangement of aldimines were investigated by using ab initio molecular dynamics simulations. Explicit molecular treatments were applied for both reactants and solvents. The reaction mechanisms were elucidated via free energy calculations based on metadynamics simulations. The results reveal that both reactions proceed in a concerted fashion. Key solvent-substrate interactions are identified from the structures of transition states with explicit solvent molecules. The remarkable promotion effect of hexafluoroisopropanol solvent is ascribed to the synergistic effect of H-bonding networks and C-H/π interactions with substrates.

Planar Hexacoordinate Beryllium: Covalent Bonding Between s-block Metals.

Achieving a planar hypercoordinate arrangement of s-block metals through covalent bonding with ligands is challenging due to the strong ionicity involved. Herein, we report the first case of a neutral binary global minimum containing a planar hexacoordinate beryllium atom. The central Be atom is coordinated by six active Be atoms, the latter in turn are enclosed by an equal number of more electronegative chlorine atoms in the periphery, forming a star-like phBe cluster (Be©Be6 Cl6 ). Importantly, the cluster exhibits dynamically stabilized stemming geometrically from the appropriate matching of metal-ligand size and electronically from adherence to the octet rule as well as possessing a 6σ/2π double aromaticity. Remarkably, energy decomposition analysis-natural orbitals for chemical valence (EDA-NOCV) analysis reveals a significant covalent interaction between the ligand and the central metal beryllium atoms, a fact further supported by a large Wiberg bond index. This cluster is a promising synthetic as its excellent electronic, dynamic and thermodynamic stability.

Origins of Regioselectivity in CuH-Catalyzed Hydrofunctionalization of Alkenes.

Factors controlling the regioselectivity in alkene hydrocupration were computationally investigated using energy decomposition analysis. The results demonstrate that the Markovnikov-selective hydrocupration with electronically activated mono-substituted olefins is mostly affected by the destabilizing Pauli repulsion, which is due to the electron delocalization effect. The anti-Markovnikov-selective hydrocupration with 1,1-dialkyl-substituted terminal olefins is dominated by the repulsive electrostatic interactions, which is because of the unequal π electron distribution caused by the induction effect of alkyl substituents.

[(OB)2-M©B7O7-BO]- (M = Mn, Tc, Re): Chemically Stable and Triply Aromatic Ballet Rotors.

Single-molecule nanorotors are generally constructed based on boron atoms to obtain structural fluxionality via possessing the delocalized multicenter bonds. However, the electron-deficient boron atoms are commonly exposed in these nanorotors, which leads to extremely high chemical reactivity, which blocks the synthesis in the condensed phase. In this work, we computationally designed a series of transition-metal-doped boron oxide clusters MB10O10- (in structural configuration of [(OB)2-M©B7O7-BO]-, M = Mn, Tc, Re, © means "centered" in a planar or quasi-planar hypercoordinate environment), which can be vividly named as "ballet rotors" to label their anthropomorphic dynamic rotational behaviors. The rotational fluxionality in ballet rotors originates from the completely delocalized nature of the bonding within their MB10 core moieties. Remarkably, compared with single-molecule nanorotors having bare boron atoms and the narrow HOMO-LUMO gaps (≤4.00 eV) as well as low vertical detachment energies (VDEs, ≤4.46 eV for anions), the ballet rotors possess significantly improved chemical stability, as evidenced sterically by the absence of exposed boron atoms and electronically by much wider HOMO-LUMO gaps (5.66-5.98 eV) as well as obviously higher VDEs between 5.36 and 5.47 eV. Specifically, the ballet rotors are mainly stabilized by the delicately placed peripheral oxygen atoms, which can compensate for all electron-deficient boron atoms via O → B π back bonds and sterically protect them. Simultaneously, they are additionally stabilized by aromatic stabilization effect from possessing the novel S + P + D triple aromaticity. We expect that the proposal of chemically stable ballet rotors in this work can arouse the rational design of nanorotors for experimental realization in the condensed phase.

[Sc©[3]CPP]+: A Viable Metal-Centered [3]Cycloparaphenylene.

[n]Cycloparaphenylenes ([n]CPPs, n denotes the number of phenyl groups) are difficult to synthesize because of the strain related to their bent phenyl rings. In particular, the strain in [3]CPP is high enough to destroy the π electron delocalization, leading to the spontaneous structural transition to an energetically more stable "bond-shift" (BS) isomer ([3]BS). In this contribution, we propose to achieve [3]CPP by enhancing the π electron delocalization through hosting a guest metal atom. Our computations revealed that Sc could stabilize [3]CPP by forming the [Sc©[3]CPP]+ complex through the favorable π-Sc donation-backdonation interactions. Thermodynamically, the binding energy between the Sc atom and [3]CPP was -205.7 kcal/mol, which could well compensate not only the energy difference of 44.2 kcal/mol between [3]CPP and [3]BS but also the extremely high strain energy of 170.3 kcal/mol in [3]CPP. Simultaneously, the [Sc©[3]CPP]+ complex is stable up to 1500 K in dynamic simulations, suggesting its high viability in the synthesis.

How hexafluoroisopropanol solvent promotes Diels-Alder cycloadditions: ab initio metadynamics simulations.

The solvent effects in Diels-Alder cycloadditions were studied by using ab initio molecular dynamics simulations with explicit molecular treatments for both substrates and solvents. Energy decomposition analysis was used to investigate the role of H-bonding networks of hexafluoroisopropanol solvent in promoting both reactivity and regioselectivity.

NAl4X4 + (X = S, Se, Te): Clusters with a planar tetracoordinate nitrogen and significantly improved stability.

The design of clusters featuring non-classical planar hypercoordinate atoms (phAs) often depends on the delocalized multicenter bonds involving reactive electron-deficient elements, which both destabilize the clusters and lead to difficulty in achieving the phA arrangement for electronegative elements such as nitrogen due to their preference for localized bonds. In this work, we computationally designed a series of aluminum chalcogenide clusters NAl4X4 + (X = S, Se, Te) with a desired planar tetracoordinate nitrogen and meaningfully improved chemical stability, as evidenced by the wide gaps (6.51-7.23 eV) between their highest occupied molecular orbitals and lowest unoccupied molecular orbitals, high molecular rigidity (dynamically stable up to 1500 K), and exclusively low global energy minima nature (their isomers locate at least 51.2 kcal/mol higher). Remarkably, these clusters are stabilized by peripheral chalcogen atoms, which not only sterically protect the NAl4 core moiety but also electronically compensate for the electron-deficient aluminum atoms via X → Al π back bonds, meeting the description of our recently proposed "electron-compensation" strategy.

Ultra-brilliant GeV betatronlike radiation from energetic electrons oscillating in frequency-downshifted laser pulses.

Electrons can be accelerated to GeV energies with high collimation via laser wakefield acceleration in the bubble regime and emit bright betatron radiation in a table-top size. However, the radiation brightness is usually limited to the third-generation synchrotron radiation facilities operating at similar photon energies. Using a two-stage plasma configuration, we propose a novel scheme for generating betatronlike radiation with an extremely high brilliance. In this scheme, the relativistic electrons inside the bubble injected from the first stage can catch up with the frequency-downshifted laser pulse formed in the second stage. The laser red shift originates from the phase modulation, together with the group velocity dispersion, which enables more energy to be transfered from the laser pulse to γ-photons, giving rise to ultra-brilliant betatronlike radiation. Multi-dimensional particle-in-cell simulations indicate that the radiated γ-photons have the cut-off energy of GeV and a peak brilliance of 1026 photons s-1 mm-2 mrad-2 per 0.1%BW at 1 MeV, which may have diverse applications in various fields.

Origin of Ligand Effects on Stereoinversion in Pd-Catalyzed Synthesis of Tetrasubstituted Olefins.

The mechanism and origin of ligand effects on stereoinversion of Pd-catalyzed synthesis of tetrasubstituted olefins were investigated using DFT calculations and the approach of energy decomposition analysis (EDA). The results reveal that the stereoselectivity-determining steps are different when employing different phosphine ligands. This is mainly due to the steric properties of ligands. With the bulkier Xantphos ligand, the syn/anti-to-Pd 1,2-migrations determine the stereoselectivity. While using the less hindered P(o-tol)3 ligand, the 1,3-migration is the stereoselectivity-determining step. The EDA results demonstrate that Pauli repulsion and polarization are the dominant factors for controlling the stereochemistry in 1,2- and 1,3-migrations, respectively. The origins of differences of Pauli repulsion and polarization between the two stereoselective transition states are further identified.

Influence of stepwise oxidation on the structure, stability, and properties of planar pentacoordinate carbon species CAl5.

Computational design has played an important role in planar hyper-coordinate carbon (phC) chemistry. However, none of numerous computationally predicted phC species were subsequently successfully synthesized in the condensed phase, perhaps due to the frustrating issue of oxidation. In the present work, we studied the influence of stepwise oxidation on the structure, stability, and properties of phC species using the milestone planar pentacoordinate carbon (ppC) species CAl5+ as an example. Our results indicated that the ppC structure of CAl5+ would be directly destroyed with one, two, or six O atom(s) per molecule present and indirectly with three or four O atoms, but maintained with five O atoms due to the ppC isomer of CAl5O5+ being a kinetically stable global energy minimum displaying σ and π double aromaticity. Moreover, the magnitudes of the first to fifth vertical oxygen affinities (VOAs) for CAl5+ were determined to be very high (-85.5 to -116.3 kcal mol-1), probably due to the existence of peripheral diffuse Al-Al bond(s). However, the sixth VOA was reduced significantly to -50.2 kcal mol-1, consistent with the absence of any diffuse Al-Al bond in the corresponding CAl5O5+ species. So CAl5O5+ may be insensitive to oxidation. Therefore, the ppC species D5h CAl5O5+ might be resistant to being degraded under a delicate control of oxidation level (producing five O atoms per CAl5+ molecule).

Transition-Metal Chemistry of Alkaline-Earth Elements: The Trisbenzene Complexes M(Bz)3 (M=Sr, Ba).

We report the synthesis and spectroscopic identification of the trisbenzene complexes of strontium and barium M(Bz)3 (M=Sr, Ba) in low-temperature Ne matrix. Both complexes are characterized by a D3 symmetric structure involving three equivalent η6 -bound benzene ligands and a closed-shell singlet electronic ground state. The analysis of the electronic structure shows that the complexes exhibit metal-ligand bonds that are typical for transition metal compounds. The chemical bonds can be explained in terms of weak donation from the π MOs of benzene ligands into the vacant (n-1)d AOs of M and strong backdonation from the occupied (n-1)d AO of M into vacant π* MOs of benzene ligands. The metals in these 20-electron complexes have 18 effective valence electrons, and, thus, fulfill the 18-electron rule if only the metal-ligand bonding electrons are counted. The results suggest that the heavier alkaline earth atoms exhibit the full bonding scenario of transition metals.

CB3E2q (q = ±1): a family of "hyparene" analogues with a planar pentacoordinate carbon.

A CB3 moiety extracted from the building units of milestone "hyparenes" (families of species with a planar pentacoordinate carbon (ppC)) was found to be a more basic building block, which can be employed to design a family of "hyparene" analogues CB3E2q (q = ±1) also with a ppC. The majority of main group elements can feasibly serve as the E atom. Despite the number of valence electrons, the ppC atoms in the CB3E2q (q = ±1) species were involved in three delocalized σ orbitals and a delocalized π orbital, so the carbon atom obeys the octet rule. The NICS studies indicated that these ppC structures are σ and π double aromatic. Given that most of them are less favourable in energy than their boron-centered isomers, it is remarkable that the global minimum of CB3Mg2- adopts the ppC arrangement. Such a ppC structure is also kinetically stable. Compared to previously reported anionic ppC global minima, CB3Mg2- does not contain hyper toxic beryllium and thus is much more attractive to our experimental colleagues for realizing the ppC species using negative ion photoelectron detachment spectroscopy.

Viable aromatic BenHn stars enclosing a planar hypercoordinate boron or late transition metal.

Monocyclic Bn rings can act as n-electron σ-donors to stabilize a non-classical planar hypercoordinate atom at ring center, forming wheel-like structures. Herein, we report that BenHn rings can also serve as n-electron σ-donors to construct star-like structures including B©Be6H6+ and TM©Be7H7q (TM is a group 10-12 metal with q = -1, 0, and 1, respectively) by complying with octet or 18-electron rules. Electronic structure analyses show that these species are stabilized by the σ-donation and π-backdonation between the central atom and the peripheral BenHn ring, the favorable Coulomb attraction due to the negative-positive-negative charge population pattern on the central atom, the middle Ben layer, and the outer Hn layer, as well as the σ-π double aromaticity. Importantly, three of the ten species, including B©Be6H6+, Cu©Be7H7, and Au

Charge-induced structural transition between seashell-like B29- and B29+ in 18 π-electron configurations.

Recent joint experimental and theoretical investigations have shown that seashell-like C2 B28 is the smallest neutral borospherene reported to date, while seashell-like Cs B29- (1-) as a minor isomer competes with its quasi-planar counterparts in B29- cluster beams. Extensive global minimum searches and first-principles theory calculations performed in this work indicate that with two valence electrons detached from B29-, the B29+ monocation favors a seashell-like Cs B29+ (1+) much different from Cs B29- (1-) in geometry which is overwhelmingly the global minimum of the system with three B7 heptagonal holes in the front, on the back, and at the bottom, respectively, unveiling an interesting charge-induced structural transition from Cs B29- (1-) to Cs B29+ (1+). Detailed bonding analyses show that with one less σ bond than B29- (1-), Cs B29+ (1+) also possesses nine delocalized π-bonds over its σ-skeleton on the cage surface with a σ + π double delocalization bonding pattern and follows the 2(n + 1)2 electron counting rule for 3D spherical aromaticity (n = 2). B29+ (1+) is therefore the smallest borospherene monocation reported to date which is π-isovalent with the smallest neutral borospherene C2 B28. The IR, Raman, and UV-vis spectra of B29+ (1+) are computationally simulated to facilitate its spectroscopic characterization.

Computational design of organometallic oligomers featuring 1,3-metal-carbon bonding and planar tetracoordinate carbon atoms.

Density functional theory computations (B3LYP) have been used to explore the chemistry of titanium-aromatic carbon "edge complexes" with 1,3-metal-carbon (1,3-MC) bonding between Ti and planar tetracoordinate Cß . The titanium-coordinated, end-capping chlorides are replaced with OH or SH groups to afford two series of difunctional monomers that can undergo condensation to form oxide- and sulfide-bridged oligomers. The sulfide-linked oligomers have less molecular strain and are more exergonic than the corresponding oxide-linked oligomers. The HOMO-LUMO gap of the oligomers varies with their composition and decreases with growing oligomer chain. This theoretical study is intended to enrich 1,3-MC bonding and planar tetracoordinate carbon chemistry and provide interesting ideas to experimentalists. Organometallic complexes with the TiE2 (E = OH and SH) decoration on the edge of aromatic hydrocarbons have been computationally designed, which feature 1,3-metal-carbon (1,3-MC) bonding between titanium and planar tetracoordinate ß-carbon. Condensation of these difunctional monomers by eliminating small molecules (H2O and H2S) produce chain-like oligomers. The HOMO-LUMO gaps of the oligomers decreases with growing oligomer chain, a trend that suggests possible semiconductor properties for oligomers with longer chains.

Linear, planar, and tubular molecular structures constructed by double planar tetracoordinate carbon D2hC2(BeH)4 species via hydrogen-bridged -BeH2Be- bonds.

This computational study identifies the rhombic D2hC2 (BeH)4 (2a) to be a species featuring double planar tetracoordinate carbons (ptCs). Aromaticity and the peripheral BeBeBeBe bonding around CC core contribute to the stabilization of the ptC structure. Although the ptC structure is not a global minimum, its high kinetic stability and its distinct feature of having a bonded C2 core from having two separated carbon atoms in the global minimum and other low-lying minima could make the ptC structure to be preferred if the carbon source is dominated by C2 species. The electron deficiency of the BeH group allows the ptC species to serve as building blocks to construct large/nanostructures, such as linear chains, planar sheets, and tubes, via intermolecular hydrogen-bridged bonds (HBBs). Formation of one HBB bond releases more than 30.0 kcal/mol of energy, implying the highly exothermic formation processes and the possibility to synthesize these nano-size structures.

The degree of π electron delocalization and the formation of 3D-extensible sandwich structures.

DFT B3LYP/6-31G(d) calculations were performed to examine the feasibility of graphene-like C42H18 and starbenzene C6(BeH)6 (SBz) polymers as ligands of 3D-extensible sandwich compounds (3D-ESCs) with uninterrupted sandwich arrays. The results revealed that sandwich compounds with three or more C42H18 ligands were not feasible. The possible reason may be the localization of π electrons on certain C6 hexagons due to π-metal interactions, which makes the whole ligand lose its electronic structure basis (higher degree of π electron delocalization) to maintain the planar structure. For comparison, with the aid of benzene (Bz) molecules, the SBz polymers can be feasible ligands for designing 3D-ESCs because the C-Be interactions in individual SBz are largely ionic, which will deter the π electrons on one C6 ring from connecting to those on neighbouring C6 rings. This means that high degree of π electron delocalization is not necessary for maintaining the planarity of SBz polymers. Such a locally delocalized π electron structure is desirable for the ligands of 3D-ESCs. Remarkably, the formation of a sandwich compound with SBz is thermodynamically more favourable than that found for bis(Bz)chromium. The assembly of 3D-ESCs is largely exothermic, which will facilitate future experimental synthesis. The different variation trends on the HOMO-LUMO gaps in different directions (relative to the sandwich axes) suggest that they can be developed to form directional conductors or semiconductors, which may be useful in the production of electronic devices.