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The structures reported in the Cambridge Structural Database (CSD) for neutral metallacycles formed by coinage metals in their valence (I) (cations) and pyrazolate anions were examined. Depending on the metal, dimers and trimers are the most common but some larger rings have also been reported, although some of the larger structures are not devoid of ambiguity. M06-2x calculations were carried out on simplified structures (without C-substituents on the pyrazolate rings) in order to facilitate a comparison with the reported X-ray structures (geometries and energies). The problems of stability of the different ring sizes were also analyzed.

The geometry, energy and electron density properties of the 1:1, 1:2 and 1:3 complexes between cyclic (Py-M) 3 (M = Au, Ag and Cu) and halide ions (F - , Cl - and Br - ) were studied using Møller Plesset (MP2) computational methods. Three different configurations were explored. In two of them, the anions interact with the metal atoms in planar and apical dispositions, while in the last configuration, the anions interact with the CH(4) group of the pyrazole. The energetic results for the 1:2 and 1:3 complexes are a combination of the specific strength of the interaction plus a repulsive component due to the charge:charge coulombic term. However, stable minima structures with dissociation barriers for the anions indicate that those complexes are stable and (Py-M) 3 can hold up to three anions simultaneously. A search in the CSD confirmed the presence of (Pyrazole-Cu) 3 systems with two anions interacting in apical disposition.

Ab initio Møller-Plesset perturbation theory (MP2)/aug'-cc-pVTZ calculations have been carried out in search of complexes, molecules, and transition structures on HN(CH)SX:SCO potential energy surfaces for X = F, Cl, NC, CCH, H, and CN. Equilibrium complexes on these surfaces have C 1 symmetry, but these have binding energies that are no more than 0.5 kJ·mol -1 greater than the corresponding C s complexes which are vibrationally averaged equilibrium complexes. The binding energies of these span a narrow range and are independent of the N-C distance across the tetrel bond, but they exhibit a second-order dependence on the S-S distance across the chalcogen bond. Charge-transfer interactions stabilize all of these complexes. Only the potential energy surfaces HN(CH)SF:SCO and HN(CH)SCl:SCO have bound molecules that have short covalent N-C bonds and significantly shorter S … S chalcogen bonds compared to the complexes. Equation-of-motion coupled cluster singles and doubles (EOM-CCSD) spin-spin coupling constants 1t J(N-C) for the HN(CH)SX:SCO complexes are small and exhibit no dependence on the N-C distance, while 1c J(S-S) exhibit a second-order dependence on the S-S distance, increasing as the S-S distance decreases. Coupling constants 1t J(N-C) and 1c J(S-S) as a function of the N-C and S-S distances, respectively, in HN(CH)SF:SCO and HN(CH)SCl:SCO increase in the transition structures and then decrease in the molecules. These changes reflect the changing nature of the N … C and S … S bonds in these two systems.

Ab initio MP2/aug'-cc-pVTZ calculations have been carried out on complexes H2C═(X)P:PXH2, for X = F, Cl, OH, CN, NC, CCH, H, CH3, and BH2. Three sets of complexes have been found on the potential surfaces. Conformation A complexes have A-P···P-A approaching linearity, with A the atom of X directly bonded to P. Conformation B complexes have A-P···P linear, but the P···P═C orientation of H2C═PX may differ significantly from linearity. Conformation C complexes are unique, since the pnicogen bond involves π-electron donation and acceptance by H2C═PX. The order of binding energies of the three conformations of H2C═(X)P:PXH2 is C > A > B, with two exceptions. Although the binding energies of conformation C complexes tend to be greater than the corresponding conformation A complexes, intermolecular distances in conformation C tend to be longer than those in conformation A. Charge transfer stabilizes H2C═(X)P:PXH2 complexes. The preferred direction of charge transfer is from H2C═PX to PXH2. In conformations A and B, charge transfer occurs from a P lone pair on one molecule to an antibonding σ* orbital on the other. However, in conformation C, charge transfer occurs from the π orbital of H2C═PX to the σ*P-A orbital of PXH2, and from the lone pair on P of PXH2 through the π-hole to the π*P═C orbital of H2C═PX. Changes in charges on P upon complexation do not correlate with changes in (31)P chemical shieldings. Computed EOM-CCSD spin-spin coupling constants correlate with P-P distances. At each distance, the ordering of (1p)J(P-P) is A > B > C. Binding energies and spin-spin coupling constants of conformation A complexes of (PH2X)2, H2C═(X)P:PXH2, and (H2C═PX)2 with A-P···P-A approaching linearity have been compared. For complexes with the more electronegative substituents, binding energies are ordered (PH2X)2 > H2C═(X)P:PXH2 > (H2C═PX)2, while the order is reversed for complexes formed from the more electropositive substituents. A plot of ΔE(PH2X)2/ΔE(H2C═PX)2 versus ΔE[H2C═(X)P:PXH2]/ΔE(H2C═PX)2 indicates that there is a systematic relationship among the stabilities of these complexes. Complexes (PH2X)2 tend to have larger spin-spin coupling constants and shorter P-P distances than H2C═(X)P:PXH2, which in turn have larger coupling constants and shorter P-P distances than (H2C═PX)2, although there is some overlap. Complexes having similar P-P distances have similar values of (1p)J(P-P).

A new protocol combining classical MD simulations and DFT calculations is presented to accurately estimate the (1)H NMR chemical shifts of highly mobile guest-host systems and their thermal dependence. This strategy has been successfully applied for the hydrogen molecule trapped into C(60) fullerene, an unresolved and challenging prototypical case for which experimental values have never been reproduced. The dependence of the final values on the theoretical method and their implications to avoid over interpretation of the obtained results are carefully described.

Understanding the bonding in complexes X:BH(3-n)F(n) and X:BH(3-n)Cl(n), for X=N(2), HCN, LiCN, H(2)CNH, NF(3), NH(3) with n=0-3, is a challenging task. The trends in calculated binding energies cannot be explained in terms of any of the usual indexes, including π donation from the halogen lone pairs to the p(π) empty orbital on B, deformation energies, charge capacities, or LUMO energies, which are normally invoked to explain the higher Lewis acidity of BCl(3) relative to BF(3). The results of the high-level G3B3 ab initio calculations reported in this study suggest that the interaction energies of these complexes are determined by a combination of at least three factors. These include the decrease in the electron-accepting ability of B as a result of π donation by the halogen atom, the increase in the electron-acceptor capacity of B due to deformation of the acid, and the large increase in the deformation energy of the acid with increasing halogen substitution. The dominant effects are those derived from the electronic effects of acid deformation. Deformation not only has direct energetic consequences, which are reflected in the large differences between dissociation (D(0)) and interaction (E(int)) energies, but also leads to an enhancement of the intrinsic acidities of BH(3-n)F(n) and BH(3-n)Cl(n) moieties by lowering the LUMO energies to very different extents, consistent with the frontier orbital model of chemical reactivity. Although this lowering depends on both the number and the nature of the halogen substituents, binding energies do not systematically increase or decrease as the number of halogen atoms increases.

We report a theoretical approach, at the M05-2x/6-311+G(d) level, to explain the affinity of indazoles for nitric oxide synthases using a simplified model of porphyrin. The theoretical E(rel)=E(i) stacking-E(i) apical values correlate with the experimental inhibition percents allowing to predict that 3,7-dinitro-1H-indazole should be a good NOS inhibitor.

Ab initio calculations have been performed to obtain structures and coupling constants (1)J(N-H), (1h)J(H-N), and (2h)J(N-N) for models of proton sponges with symmetric and asymmetric N-H(+)-N intramolecular hydrogen bonds (IMHBs). For a given model, the asymmetric structure has a lower energy, a longer N-N distance, and a hydrogen bond which has a greater deviation from linearity. The computed values of (2h)J(N-N) for the models are significantly less than predicted values based on the distance dependence of (2h)J(N-N) for complexes with intermolecular N-H(+)-N hydrogen bonds. However, the reduced values of (2h)J(N-N) cannot be attributed solely to the distortion of the hydrogen bond in the models, but also reflect differences in s electron populations at the nitrogens in both the ground state and the excited states which couple to it through the Fermi-contact (FC) operator. Values of (2h)J(N-N) for IMHBs can be related quadratically to the N-N distances in the models, and demonstrate that there is no discrepancy between computed values of (2h)J(N-N) at the short N-N distances found in these systems and experimental data for proton sponges., (2008 John Wiley & Sons, Ltd.)

A theoretical study (DFT and MP2) of the self-association of homochiral (RR or SS) and heterochiral (RS or SR) dimers of three series of cyclic alpha-hydroxy-carbonyl derivatives has been carried out. The solvation effect on the parent derivative dimers has been explored, showing nonsignificant changes in the configurations preferred but altering in some cases the homo/heterochiral preference of the dimers. The results in the gas phase of the systems with different substituents show a preference for the heterochiral dimers. The energetic results have been analyzed with the NBO and AIM methodologies. Optical rotatory power calculations of the monomers and homochiral dimers show large variations of this parameter depending on the substituents and the complexation.

Molecular mechanics calculations (Macromodel v.5.0 and v.8.1) have been used in order to correlate the minimized energies of the complexes with the binding constant Kb values measured on two hosts and five urea derivatives including methyl biotin. Kb values obtained by means of NMR titrations, in the right concentration range between 20 and 80% of saturation, correlate well with the energies provided by the molecular modeling study of the complexes.

The reduced two-bond Fermi-contact terms and the reduced spin-spin coupling constants (2h)K(X-Y) across X-H-Y hydrogen bonds for complexes stabilized by C-H-N, N-H-N, O-H-N, F-H-N, C-H-O, O-H-O, F-H-O and C-H-F hydrogen bonds are positive. The NMR Triplet Wavefunction Model (NMRTWM) indicates that the signs of the reduced FC terms and (2h)K(X-Y) are determined by excited triplet states that have an odd number of nodes intersecting the X-Y axis between X and Y, thereby leading to an antiparallel alignment of the nuclear magnetic moments of atoms X and Y., (Copyright 2004 John Wiley & Sons, Ltd.)

The chiral recognition in the formation of hydrogen-bonded (HB) dimers of 1,6a-dihydropyrrolo[2,3-b]pyrrole derivatives as well as in their proton-transfer processes have been studied by means of ab initio calculations. The heterochiral dimers are in general the most stable ones, but amphiprotic substituents that are able to form attactive interactions with twin groups revert this tendency. Energy differences up to 4.0 kcal/mol have been found favoring the homo- or heterochiral complexes. Two possible proton-transfer processes have been studied, the concerted one and the nonconcerted one. The compresion of the systems in the transition structures produce an increase in the energetic differences when compared to the corresponding minima complexes. A Steiner-Limbach relationship has been found for the geometrical properties of the HB in the minima and transition states calculated here. The electron density and its Laplacian at the bond critical point have been found to correlate with the HB distance.