In Silico Design and Characterization of a New Molecular Electride: Li@Calix[3]Pyrrole.

Electrides, in which anionic electrons are localized independently of the atoms in the compound, have shown promise, especially as catalysts and optoelectronic materials. Here, we present a new computationally designed molecular electride, Li@calix[3]pyrrole (Li@C3P). Electron density and electron localization function analyses unequivocally confirm the existence of localized electride electron density, outside the system, independent of any specific atoms. Non-covalent interaction plots further validate the character of the isolated localized electron, suggesting that the system can be accurately represented by Li+@calix[3]pyrrole ⋅ e-, denoting its distinct charge separation. The remarkable non-linear optical properties of Li@C3P, including average polarizability, α ‾ ${\bar{\alpha }}$ =412.4 au, first hyperpolarizability, ß=4.46×104 au, and second hyperpolarizability, γ ∥ ${{\gamma }_{\parallel }}$ =18.40×106 au, are unparalleled in the previously reported and similar Li@C4P molecular electride. Furthermore, energy decomposition analysis in combination with natural orbital for chemical valence theory sheds light on the mechanism of electron density transfer from Li to the C3P cage, yielding the charge-separated Li@C3P complex. In addition to the electron transfer, a key factor to its electride nature is the electronic structure of the CnP cage, which has its lowest unoccupied molecular orbital located in the void adjacent to the N-H groups at the back of the bowl-shaped CnP cage.

Defect-Free Synthesis of a Fully π-Conjugated Helical Ladder Polymer and Resolution into a Pair of Enantiomeric Helical Ladders.

Fully π-conjugated ladder polymers with a spiral geometry represent a new class of helical polymers with great potential for organic nanodevices, but there is no precedent for an optically active helical ladder polymer totally composed of achiral units. We now report the defect-free synthesis and resolution of a fully π-conjugated helical ladder polymer with a rigid helical cavity, which has been achieved by quantitative and chemoselective acid-promoted alkyne benzannulations of a rationally designed, random-coil achiral polymer followed by chromatographic enantioseparation. Because of a sufficiently high helix-inversion barrier, the isolated excess one-handed helical ladder polymer with a degree of polymerization of more than 15 showed a strong circular dichroism with a dissymmetry factor of up to 1.7×10-2 and is thermally stable, maintaining its optical activity in solution even at 100 °C, as well-supported by molecular dynamics simulation.

Chiral Calix[3]pyrrole Derivatives: Synthesis, Racemization Kinetics, and Ring Expansion to Calix[9]- and Calix[12]pyrrole Analogues.

Chiral pyrrolic macrocycles continue to attract interest. However, their molecular design remains challenging. Here, we report a calixpyrrole-based chiral macrocyclic system, calix[1]furan[1]pyrrole[1]thiophene (1), synthesized from an oligoketone. Macrocycle 1 adopts a partial cone conformation in the solid state, and undergoes racemization via ring inversion. Molecular dynamics simulations revealed that inversion of the thiophene is the rate determining step. Pyrrole N-methylation suppressed racemization and permitted chiral resolution. Enantioselective N-methylation also occurred in the presence of a chiral ammonium salt, although the stereoselectivity is modest. A unique feature of 1 is that it acts as a useful synthetic precursor to yield several calix[n]furan[n]pyrrole[n]thiophene products (n=2-4), including a calix[12]pyrrole analogue that to our knowledge constitutes the largest calix[n]pyrrole-like species to be structurally characterized.

One-Handed Helical Tubular Ladder Polymers for Chromatographic Enantioseparation.

Defect-free one-handed contracted helical tubular ladder polymers with a π-electron-rich cylindrical helical cavity were synthesized by alkyne benzannulations of the random-coil precursor polymers containing 6,6'-linked-1,1'-spirobiindane-7,7'-diol-based chiral monomer units. The resulting tightly-twisted helical tubular ladder polymers showed remarkably high enantioseparation abilities toward a variety of chiral hydrophobic aromatics with point, axial, and planar chiralities. The random-coil precursor polymer and analogous rigid-rod extended helical ribbon-like ladder polymer with no internal helical cavity exhibited no resolution abilities. The molecular dynamics simulations suggested that the π-electron-rich cylindrical helical cavity formed in the tightly-twisted tubular helical ladder structures is of key importance for producing the highly-enantioseparation ability, by which chiral aromatics can be enantioselectively encapsulated by specific π-π and/or hydrophobic interactions.

Molecular Electrides: An In Silico Perspective.

Electrides are defined as the ionic compounds where the electron(s) serves as an anion. These electron(s) is (are) not bound to any atoms, bonds, or molecules but are rather localized into the space, crystal voids, or interlayer between two molecular slabs. There are three major categories of electrides, known as organic electrides, inorganic electrides, and molecular electrides. The computational techniques have proven as a great tool to provide emphasis on the electride materials. In this review, we have focused on the computational methodologies and criteria that help to characterize molecular electrides. A detailed account of the computational methods and basis sets applicable for molecular electrides have been discussed along with their limitations in this field. The main criterion for the identification of the electrides has also been discussed thoroughly with proper examples. The molecular electrides presented here have been justified with all the required criteria that support and proved their electride characteristics. We have also presented few systems which have similar properties but are not considered as molecular electrides. Moreover, the applicability of the electrides in catalytic processes have also been presented.

DNA-Mimicking Metal-Organic Frameworks with Accessible Adenine Faces for Complementary Base Pairing.

Biologically derived metal-organic frameworks (Bio-MOFs) are significant, as they can be used in cutting-edge biomedical applications such as targeted gene delivery. Herein, adenine (Ade) and unnatural amino acids coordinate with Zn2+ to produce biocompatible frameworks, KBM-1 and KBM-2, with extremely defined porous channels. They feature an accessible Watson-Crick Ade face that is available for further hydrogen bonding and can load single-stranded DNA (ssDNA) with 13 and 41% efficiency for KBM-1 and KBM-2, respectively. Treatment of these frameworks with thymine (Thy), as a competitive guest for base pairing with the Ade open sites, led to more than 50% reduction of ssDNA loading. Moreover, KBM-2 loaded Thy-rich ssDNA more efficiently than Thy-free ssDNA. These findings support the role of the Thy-Ade base pairing in promoting ssDNA loading. Furthermore, theoretical calculations using the self-consistent charge density functional tight-binding (SCC-DFTB) method verified the role of hydrogen bonding and van der Waals type interactions in this host-guest interface. KBM-1 and KBM-2 can protect ssDNA from enzymatic degradation and release it at acidic pH. Most importantly, these biocompatible frameworks can efficiently deliver genetic cargo with retained activity to the cell nucleus. We envisage that this class of Bio-MOFs can find immediate applicability as biomimics for sensing, stabilizing, and delivering genetic materials.

Intriguing structural, bonding and reactivity features in some beryllium containing complexes.

Although the toxicity of beryllium compounds causes impediments in experiments involving them, beryllium chemistry has seen a recent upsurge of interest and considerable progress. Computations play a very important complementary role in analyzing the structure, stability and bonding of these compounds. In this perspective article, we highlighted our contribution to beryllium chemistry which is either completely through theoretical results or sometimes supported by experimental findings. It starts with the smallest 2π aromatic system, Be32-, which also exhibits rare bond-stretch isomerism. Furthermore, its reactivity towards different transformations is mentioned. Because of the ability of beryllium to attain a high ionic potential, the beryllium center in an appropriate situation can act as an excellent Lewis acid which is utilized to bind noble gas (Ng) atoms, carbon monoxide and dinitrogen through donor-acceptor types of interactions. We made several efforts to have strong Ng-Be bonds which led us to NgBeNCN that is recorded to have the strongest Ng-Be bond among the neutral Ng-Be complexes reported so far. Significant dinitrogen activation was also achieved in (NN)2Be(η2-N2) and OCBeNN complexes. In the latter case, a complete cleavage of the N-N bond producing the most stable NBeNCO molecule has occurred. We also found viable M2(NHBMe)2 (M = Be, Mg) complexes having unusual bonding where the interacting fragments are best described as the neutral M2 and (NHBMe)2 but M2 still possesses a single bond. We finally discussed the complex comprising an unusual Be(i) oxidation state, [BeI(cAACAr)2]+˙ and di-ortho-beryllated carbodiphosphorane exhibiting Be⇇C double dative bonds.

Two Closely Related Zn(II)-MOFs for Their Large Difference in CO2 Uptake Capacities and Selective CO2 Sorption.

Two azo functionalized Zn(II)-based MOFs, {[Zn(SDB)(3,3'-L)0.5]·xG}n, IITKGP-13A, and {[Zn2(SDB)2(4,4'-L)]·xG}n, IITKGP-13B (IITKGP stands for Indian Institute of Technology Kharagpur), have been constructed through the self-assembly of isomeric N,N'-donor spacers (3,3'-L = 3,3'-azobispyridine and 4,4'-L = 4,4'-azobispyridine) with organic ligand 4,4'-sulfonyldibenzoic acid (SDBH2) and Zn(NO3)2·6H2O (G represents disordered solvent molecules). Single-crystal X-ray diffraction studies reveal the 2D structure with sql topology for both MOFs. However, the subtle change in positions of coordinating N atoms of spacers makes IITKGP-13A noninterpenetrated, while IITKGP-13B bears a 2-fold interpenetrated structure. IITKGP-13A exhibits higher uptake of CO2 over CH4 and N2 with high IAST selectivities for mixed CO2/CH4 (50:50, biogas) and CO2/N2 (15:85, flue gas) gas systems. In contrast, IITKGP-13B takes up very low amount of CO2 gas (0.4 mmol g-1) compared to IITKGP-13A (1.65 mmol g-1) at 295 K. Density functional theory (DFT)-based electronic structure calculations have been performed to explain the origin of the large differences in CO2 uptake capacity between the two MOFs at the atomistic level. The results show that the value of the change in enthalpy (ΔH) at 298 K temperature and 1 bar pressure for the CO2 adsorption is more negative in IITKGP-13A as compared to that in IITKGP-13B, thus indicating that CO2 molecules are more favored to get adsorbed in IITKGP-13A than in IITKGP-13B. The computed values for the Gibbs' free energy change (ΔG) for the CO2 adsorption are positive for both of the MOFs, but a higher value is observed for the IITKGP-13B. The noncovalent types of interactions are the main contribution toward the attractive energies between the host MOF frameworks and guest CO2 molecules, which has been studied with the help of energy decomposition analysis (EDA).

Encapsulation of Mg2 inside a C60 cage forms an electride.

Density functional theory (DFT) based calculations have been carried out for the endohedral encapsulation of magnesium dimer inside fullerene, that is, Mg2 @C60 . It is observed that the minimum energy structure of the Mg2 @C60 system is C2h symmetry. The MgMg bond distance in the Mg2 @C60 system is much shorter than that in the free Mg2 and Mg2 2+ ion. The formation of the endohedral Mg2 @C60 system is thermochemically spontaneous in nature. The natural bond orbital (NBO) analysis showed the presence of an Mg2 2+ fragment with an MgMg bond inside the C60 cage. The electron density descriptors have identified the covalency in the MgMg bond. A non-nuclear attractor (NNA) is present in the middle of the two Mg-atoms. The bonding interaction between the Mg2 and C60 fragments is ionic in nature and the [Mg2 2+ ] and [C60 2- ] represent the bonding pattern in the Mg2 @C60 system. The designed endohedrally encapsulated system behaves as an electride.

Metal-Organic Frameworks of Cu(II) Constructed from Functionalized Ligands for High Capacity H2 and CO2 Gas Adsorption and Catalytic Studies.

Two Cu(II)-based metal-organic frameworks (MOFs) having paddle-wheel secondary building units (SBUs), namely, 1Me and 1ipr, were synthesized solvothermally using two new bent di-isophthalate ligands incorporating different substituents. The MOFs showed high porosity (BET surface area, 2191 m2/g for 1Me and 1402 m2/g for 1ipr). For 1Me, very high CO2 adsorption (98.5 wt % at 195 K, 42.9 wt % at 273 K, 23.3 wt % at 298 K) at 1 bar was found, while for 1ipr, it was significantly less (14.3 wt % at 298 K and 1 bar, 54.4 wt % at 298 K at 50 bar). 1Me exhibited H2 uptake of 3.2 wt % at 77 K and 1 bar of pressure, which compares well with other benchmark MOFs. For 1ipr, the H2 uptake was found to be 2.54 wt % under similar experimental conditions. The significant adsorption of H2 and CO2 for 1Me could be due to the presence of micropores as well as unsaturated metal sites in these MOFs besides the presence of substituents that interact with the gas molecules. The experimental adsorption behavior of the MOFs could be justified by theoretical calculations. Additionally, catalytic conversions of CO2 and CS2 into useful chemicals like cyclic carbonates, cyclic trithiocarbonates, and cyclic dithiocarbonates could be achieved.

Flexibility Induced Encapsulation of Ultrafine Palladium Nanoparticles into Organic Cages for Tsuji-Trost Allylation.

A series of three positional isomers of organic cages namely o-OC, m-OC, and p-OC, have been self-assembled using dynamic covalent chemistry. Their room temperature controlled fabrication with palladium gives ultrafine diameter (1-2 nm) of palladium nanoparticles (Pd NPs). We observed that the shape-flexibility of cages have great impact on the formation of Pd NPs. Theoretical calculations reveals that theoretically obtainable size of Pd NPs for each cage which was complementary to the experimental results. Theoretical studies indicate that the driving forces for the specific orientational preference may be ascribed to subtle variations on the level of π-π interactions, which ultimately governs the growth of Pd NPs therein. It is the first example of shape-flexible synthesis of organic cages where flexibility governs the nanoparticle growth. Pd NPs have shown excellent catalysis of Tsuji-Trost allylation at room temperature and pressure in water.

Filling the void: controlled donor-acceptor interaction facilitates the formation of an M-M single bond in the zero oxidation state of M (M = Zn, Cd, Hg).

The intriguing question of whether it is possible to form a genuine M0-M0 single bond for the M2 species (M = Zn, Cd, Hg) is addressed here. So far, all the bonds reported in the literature are exclusively MI-MI. Herein, we present viable M2(NHBMe)2 (M = Zn, Cd, Hg; NHBMe = (HCNMe)2B) complexes in which the controlled donor-acceptor interaction leads to an M0-M0 single bond. In these complexes, M2 in the 1∑g ground state with the (nσg+)2(nσu+)2 (n = 7, 10 and 14 for M = Zn, Cd and Hg, respectively) valence electron configuration forms donor-acceptor bonding with singlet 2NHBMe ligands where a combined effect of dominant (+,-) σ-backdonation from the antibonding (nσu+)2 orbital of M2 to the 2NHBMe ligands and a somewhat weaker (+,+) σ-donation from the 2NHBMe ligands to the bonding (n + 1)σg+ orbital leads to the unorthodox bonding situation of forming an M-M single bond in the zero oxidation state by eventually nullifying one effect by another. This is an unprecedented situation in the sense that the NHBMe ligand acts as a strong σ-acceptor and a weaker σ-donor. A comparison with the experimentally reported M2(PhDipp)2 complexes reveals the uniqueness of the NHBMe ligand in exhibiting such a bonding scenario. The M2(NHBMe)2 complex is thermochemically viable with respect to possible dissociation channels at room temperature, except for metal extrusion processes, M2(NHBMe)2 → M + M(NHBMe)2 and M2(NHBMe)2 → M2 + (NHBMe)2. Although the latter two processes are exergonic, they are kinetically protected by a high free energy barrier of 26.5-39.5 kcal mol-1. The experimental characterization of M2(PhDipp)2 despite similar exergonic channels reveals such kinetic stability to be enough for the viability of the M2(NHBMe)2 complexes. Furthermore, the ligand exchange reaction considering M2(PhMe)2 as the starting material also turned out to be feasible. Therefore, the M2(NHBMe)2 complexes are the first cases that feature a neutral M2 moiety with a single M0-M0 covalent bond, where M is a Group 12 metal.

How Far Can One Push the Noble Gases Towards Bonding?: A Personal Account.

Noble gases (Ngs) are the least reactive elements in the periodic table towards chemical bond formation when compared with other elements because of their completely filled valence electronic configuration. Very often, extreme conditions like low temperatures, high pressures and very reactive reagents are required for them to form meaningful chemical bonds with other elements. In this personal account, we summarize our works to date on Ng complexes where we attempted to theoretically predict viable Ng complexes having strong bonding to synthesize them under close to ambient conditions. Our works cover three different types of Ng complexes, viz., non-insertion of NgXY type, insertion of XNgY type and Ng encapsulated cage complexes where X and Y can represent any atom or group of atoms. While the first category of Ng complexes can be thermochemically stable at a certain temperature depending on the strength of the Ng-X bond, the latter two categories are kinetically stable, and therefore, their viability and the corresponding conditions depend on the size of the activation barrier associated with the release of Ng atom(s). Our major focus was devoted to understand the bonding situation in these complexes by employing the available state-of-the-art theoretic tools like natural bond orbital, electron density, and energy decomposition analyses in combination with the natural orbital for chemical valence theory. Intriguingly, these three types of complexes represent three different types of bonding scenarios. In NgXY, the strength of the donor-acceptor Ng→XY interaction depends on the polarizing power of binding the X center to draw the rather rigid electron density of Ng towards itself, and sometimes involvement of such orbitals becomes large enough, particularly for heavier Ng elements, to consider them as covalent bonds. On the other hand, in most of the XNgY cases, Ng forms an electron-shared covalent bond with X while interacting electrostatically with Y representing itself as [XNg]+Y-. Nevertheless, in some of the rare cases like NCNgNSi, both the C-Ng and Ng-N bonds can be represented as electron-shared covalent bonds. On the other hand, a cage host is an excellent moiety to examine the limits that can be pushed to attain bonding between two Ng atoms (even for He) at high pressure. The confinement effect by a small cage-like B12N12 can even induce some covalent interaction within two He atoms in the He2@B12N12 complex.

Unprecedented Bonding Situation in Viable E2 (NHBMe )2 (E=Be, Mg; NHBMe =(HCNMe )2 B) Complexes: Neutral E2 Forms a Single E-E Covalent Bond.

Is it possible to facilitate the formation of a genuine Be-Be or Mg-Mg single bond for the E2 species while it is in its neutral state? So far, (NHCR )Be-Be(NHCR ) (R=H, Me, Ph) have been reported where Be2 is in 1 Δg excited state imposing a formal Be-Be bond order of two. Herein, we present the formation of a single E-E (E=Be, Mg) covalent bond in E2 (NHBMe )2 (E=Be, Mg; NHBMe =(HCNMe )2 B) complexes where E2 is in 3 ∑u + excited state having (nσg + )2 (nσu + )1 ((n+1)σg + )1 (n=2 for Be and n=4 for Mg) valence electron configuration and it forms electron-shared bonding with two NHBMe radicals. The effects of bonding with nσu + and (n+1)σg + orbitals will cancel each other, providing the former E-E bond order as one. Be2 (NHBMe )2 complex is thermochemically stable with respect to possible dissociation channels at room temperature, whereas the two exergonic channels, Mg2 (NHBMe )2 → Mg + Mg(NHBMe )2 and Mg2 (NHBMe )2 → Mg2 + (NHBMe )2 , are kinetically inhibited by a free energy barrier of 15.7 and 18.7 kcal mol-1 , respectively, which would likely to be further enhanced in cases of bulkier substituents attached to the NHB ligands. Therefore, the title complexes are first viable systems which feature a neutral E2 moiety with a single E-E covalent bond.

Stabilization of Boron-Boron Triple Bonds by Mesoionic Carbenes.

Density functional theory-based computations are carried out to analyze the electronic structure and stability of B2(MIC)2 complexes, where MIC is a mesoionic carbene, viz., imidazolin-4-ylidenes, pyrazolin-4-ylidene, 1,2,3-triazol-5-ylidene, tetrazol-5-ylidene, and isoxazol-4-ylidene. The structure, stability, and the nature of bonding of these complexes are further compared to those of the previously reported B2(NHC)2 and B2(cAAC)2. A thorough bonding analysis via natural bond order, molecular orbital, and energy decomposition analyses (EDA) in combination with natural orbital for chemical valence (NOCV) reveals that MICs are suitable ligands to stabilize B2 species in its (3)1∑g + excited state, resulting in an effective B-B bond order of 3. Their high dissociation energy and endergonicity at 298 K for the dissociations L-BB-L → 2 B-L and L-BB-L → BB + 2 L (L = Ligand) indicate their viability at ambient condition. The donor property of MICs is comparable to that of NHCMe. The orbital interaction plays a greater role than the coulombic interaction in forming the B-L bonds. The EDA-NOCV results show that the sum of the orbital energies associated with the (+, +) and (+, -) L→[B2]←L σ-donations is far larger than that of L←[B2]→L π-back donation. It also reveals that cAACMe possesses the largest σ-donation and π-back donation abilities among the studied ligands, and the σ-donation and π-back donation abilities of MICs are comparable to those of NHCMe. Therefore, the present study shows that MICs would also be an excellent choice as ligands to experimentally realize new compounds having a strong B-B triple bond.

Activation of Small Molecules (H2, CO2, N2O, CH4, and C6H6) by a Porphyrinoid-Based Dimagnesium(I) Complex, an Electride.

A density functional theory-based computation has been carried out to reveal the geometrical and electronic structures of Mg2EP (1), where EP is an extended (3.1.3.1) porphyrinoid system. EP is a 22 π electronic system and is aromatic in nature. Here, we have studied the thermodynamic and kinetic stabilities of EP2--supported Mg2 2+ ion. The nature of bonding has been studied using natural bond orbital and atoms in molecule schemes. The presence of a covalent Mg(I)-Mg(I) σ-bond in Mg2EP is confirmed. The occurrence of a non-nuclear attractor (NNA) with large electron population, negative Laplacian of electron density at NNA, and presence of an electron localization function basin along with large nonlinear optical properties prompt us to classify Mg2EP as the first porphyrinoid-based organic electride. Further five small molecules, viz., dihydrogen (H2), carbon dioxide (CO2), nitrous oxide (N2O), methane (CH4), and benzene (C6H6), are found to be activated by the electron density between the two Mg atoms in Mg2EP.

Boron Nanowheels with Axles Containing Noble Gas Atoms: Viable Noble Gas Bound M©B10- Clusters (M=Nb, Ta).

The viability of noble gas axled boron nanowheels Ngn M©B10- (Ng=Ar-Rn; M=Nb, Ta; n=1, 2) is explored by ab initio computations. In the resulting Ng2 -M complexes, the Ng-M-Ng nanorod passes through the center of the B10- ring, providing them with an inverse sandwich-like structure. While in the singly Ng bound analogue, the Ng binding enthalpy Hb at 298 K ranges from 2.5 to 10.6 kcal mol-1 , in doubly Ng bound cases it becomes very low for the Ng2 M©B10- →Ng+NgM©B10- dissociation channel, except for the case of Rn, for which the corresponding Hb values are 3.4 (Nb) and 4.0 kcal mol-1 (Ta). For a given Ng, Ta has slightly higher Ng-binding ability than Nb. The corresponding free-energy changes indicate that these systems, particularly the Xe and Rn complexes, are good candidates for experimental realization in a low-temperature matrix. The Ng-M bonds were found to be covalent in nature, as reflected in their large Wiberg bond indices, formation of a 2c-2e σ orbital between Ng and M centers in natural bond orbital and adaptive natural density partitioning (AdNDP) analyses, and the short Ng-M distances. Energy decomposition analysis and a study on the natural orbitals for chemical valence show that the Ng-M contact is supported mainly by the orbital and electrostatic interactions, with almost equal contributions. Although both the Ng→M σ donation and Ng←M π backdonation play roles in the origin of orbital interaction, the former is significantly dominant over the latter. Further, AdNDP analysis indicates that the doubly aromatic character (both σ and π) in MB10- clusters is not perturbed by the interaction with Ng atoms.

A Cu(ii)-MOF capable of fixing CO2 from air and showing high capacity H2 and CO2 adsorption.

A porous Cu(ii)-MOF shows an adsorption of 6.6 wt% of H2 at 77 K and 62 bar and a very high 60 wt% of CO2 at 298 K and 32 bar. When air is bubbled into a suspension of the activated MOF in the presence of different epoxides at room temperature, the CO2 in air is readily converted into the corresponding cyclic carbonates.

A Spinning Umbrella: Carbon Monoxide and Dinitrogen Bound MB12- Clusters (M = Co, Rh, Ir).

Strong binding of carbon monoxide (CO) and dinitrogen (N2) by MB12- (M = Co, Rh, Ir) clusters results in a spinning umbrella-like structure. For OCMB12- and NNMB12- complexes, the bond dissociation energy values range within 50.3-67.7 kcal/mol and 25.9-35.7 kcal/mol, respectively, with the maximum value obtained in Ir followed by that in Co and Rh analogues. COMB12- complex is significantly less stable than the corresponding C-side bonded isomer. The associated dissociation processes for OCMB12- and NNMB12- into CO or N2 and MB12- are highly endergonic in nature at 298 K, implying their high thermochemical stability with respect to dissociation. In OCMB12- and NNMB12- complexes, the C-O and N-N bonds are found to be elongated by 0.022-0.035 Å along with a large red-shift in the corresponding stretching frequencies, highlighting the occurrence of bond activation therein toward further reactivity due to complexation. The obtained red-shift is explained by the dominance of L←M π-back-donation (L = CO, OC, NN) over L→M σ-donation. The binding of L enhances the energy barrier for the rotation of the inner B3 unit within the outer B9 ring by 0.4-1.8 kcal/mol, which can be explained by a reduction in the distance of the longest bond between inner B3 and outer B9 rings upon complexation. A good correlation is found between the change in rotational barrier relative to that in MB12- and the energy associated with the L→M σ-donation. Born-Oppenheimer molecular dynamics simulations further support that the M-L bonds in the studied systems are kinetically stable enough to retain the original forms during the internal rotation of inner B3 unit.

NgMCp+: Noble Gas Bound Half-Sandwich Complexes (Ng = He-Rn, M = Be-Ba, and Cp = η5-C5H5).

Structures, bonding, and stability of half-sandwich complexes with general formula, NgMCp+ (Ng = He-Rn, M = Be-Ba, Cp = η5-C5H5) are analyzed through ab initio computation. MCp+ complexes possess remarkable Ng binding ability, particularly for M = Be and Mg. While for Ar-Rn bound analogues the bond dissociation energy in the former complex ranges within 17.5-28.0 kcal mol-1, it becomes 10.4-18.7 kcal mol-1 in the latter complex. In fact, BeCp+ is able to form a strong bond with the two most inert elements, He and Ne. Although the Ng binding ability of MCp+ gradually diminishes in moving from Be to Ba, the corresponding free energy change values show that Kr-Rn bound complexes involving the heavier congeners of Mg would remain in the bound state avoiding dissociation into Ng and MCp+. The nature of the Ng-M bond is characterized by natural bond orbital, electron density and energy decomposition analyses in conjunction with the natural orbital for chemical valence (EDA-NOCV) analysis. While the electron density analysis reveals that Ng-Be (Ng = Kr, Xe, Rn) and Ng-Mg (Ng = Xe, Rn) bonds are partly covalent in nature, the orbital interaction (ΔEorb) is found to be the most important term in the Ng-M attractive energy as revealed by the EDA-NOCV. For all Ngs, the major contribution toward the ΔEorb energy term originates from Ng→MCp+ σ-donation. Additionally, CpBeNgF (Ng = Xe, Rn) and CpNgF (Ng = Kr-Rn) are found to be viable systems with kinetic protection for the exergonic dissociation channels, CpBeNgF → Ng + CpBeF and CpNgF → Ng + CpF, respectively, where the activation free energy barrier in the latter systems (24.1-34.7 kcal mol-1) is significantly larger than that in the former ones (6.6-8.9 kcal mol-1). CpNgF (Ng = Kr-Rn) complexes are predicted to be stable even above 300 K, whereas CpBeNgF (Ng = Xe, Rn) would be viable up to ∼100 K. While the F-Ng bonds are ionic in nature, the Ng-Be and Ng-C bonds in these complexes have significant covalent character.