A single tripodal ligand stabilizing three different oxidation states (II, III, and IV) of manganese.

A series of mononuclear Mn(II), Mn(III), and Mn(IV) complexes was prepared using a single tripodal ligand (H(3)L). Addition of a cation (NH(4)(+), K(+), Na(+)) to [Mn(III)L] showed a pronounced effect on the redox potentials. Different variants of Jahn-Teller distortion, axial elongation and compression, were observed in the Mn(III) complexes.

Significance of ammonia in growth of atmospheric nanoclusters.

We apply accurate quantum chemistry methods to study the thermochemistry of molecular clusters containing ammonia, water, and sulfuric acid and investigate initial reaction steps in atmospheric nucleation by calculating free energies for the related reactions. The results indicate that ammonia is a key reactant enhancing the growth of small water-sulfuric acid clusters in atmospheric conditions. The role of ammonia becomes significant when the nanoclusters contain more than one or two sulfuric acid molecules. This implies a lower limit of 1:3 for the NH3/H2SO4 mole ratio of atmospheric sulfuric acid-water-ammonia clusters.

Ab initio and density functional theory reinvestigation of gas-phase sulfuric acid monohydrate and ammonium hydrogen sulfate.

We have calculated the thermochemical parameters for the reactions H(2)SO(4) + H(2)O <--> H(2)SO(4).H(2)O and H(2)SO(4) + NH(3) <--> H(2)SO(4).NH(3) using the B3LYP and PW91 functionals, MP2 perturbation theory and four different basis sets. Different methods and basis sets yield very different results with respect to, for example, the reaction free energies. A large part, but not all, of these differences are caused by basis set superposition error (BSSE), which is on the order of 1-3 kcal mol(-1) for most method/basis set combinations used in previous studies. Complete basis set extrapolation (CBS) calculations using the cc-pV(X+d)Z and aug-cc-pV(X+d)Z basis sets (with X = D, T, Q) at the B3LYP level indicate that if BSSE errors of less than 0.2 kcal mol(-1) are desired in uncorrected calculations, basis sets of at least aug-cc-pV(T+d)Z quality should be used. The use of additional augmented basis functions is also shown to be important, as the BSSE error is significant for the nonaugmented basis sets even at the quadruple-zeta level. The effect of anharmonic corrections to the zero-point energies and thermal contributions to the free energy are shown to be around 0.4 kcal mol(-1) for the H(2)SO(4).H(2)O cluster at 298 K. Single-point CCSD(T) calculations for the H(2)SO(4).H(2)O cluster also indicate that B3LYP and MP2 calculations reproduce the CCSD(T) energies well, whereas the PW91 results are significantly overbinding. However, basis-set limit extrapolations at the CCSD(T) level indicate that the B3LYP binding energies are too low by ca. 1-2 kcal/mol. This probably explains the difference of about 2 kcal mol(-1) for the free energy of the H(2)SO(4) + H(2)O <--> H(2)SO(4).H(2)O reaction between the counterpoise-corrected B3LYP calculations with large basis sets and the diffusion-based experimental values of S. M. Ball, D. R. Hanson, F. L Eisele and P. H. McMurry (J. Phys. Chem. A. 2000, 104, 1715). Topological analysis of the electronic charge density based on the quantum theory of atoms in molecules (QTAIM) shows that different method/basis set combinations lead to qualitatively different bonding patterns for the H(2)SO(4).NH(3) cluster. Using QTAIM analysis, we have also defined a proton transfer degree parameter which may be useful in further studies.

Chemical structures from the analysis of domain-averaged fermi holes. Nature of the Mn-Mn bond in bis(pentacarbonylmanganese).

Because of conflicting and contradictory classification based on traditional AIM characteristics, the nature of the Mn-Mn bond has been and still is the subject of continuing discussions. To overcome the existing inconsistencies in the interpretation of the nature of this bond, the bonding in Mn2(CO)10 has been analyzed and discussed in terms of new recently proposed methodology known as the analysis of domain-averaged Fermi holes. It has been shown that this analysis is able to reconcile the conflicting conclusions of earlier AIM-based studies with traditional anticipations based on simple electron counting rules. According to Fermi hole analysis, the Mn-Mn bond has the character of the more or less ordinary covalent single sigma bond, but the analysis also brings clear evidence in favor of Mn . . . (CO) intramolecular interactions between the metal atom and the ligands bonded to the other metal atom. These interactions could be responsible for the observed decrease of electron density at the bond critical point detected in AIM studies.

Aurophilicity-coordination interplay in the design of cyano-bridged nickel(II)-Gold(I) bimetallic assemblies: structural and computational studies of the gold(I)-gold(I) interactions.

Two polymorphic cyano-bridged Au(I)-Ni(II) bimetallic complexes of formulas [Ni(en)2Au(CN)2][Au(CN)2] (1) and [Ni(en)2[Au(CN)2]2] (2) have been prepared from the 1:2 reaction between [Au(CN)2]- and either [Ni(en)2Cl2]Cl or [Ni(en)3]Cl2.2H2O, respectively. The structure of 1 consists of polymeric cationic chains of alternating [Au(CN)2]- and [Ni(en)2]2+ units running along the a axis and [Au(CN)2]- anions lying between the chains. The noncoordinated dicyanoaurate anions are aligned perpendicular to the ac plane and involved in aurophilic interactions with the bridging dicyanoaurate groups, ultimately leading to a 2D bimetallic grid. The structure of 2 consists of trinuclear molecules made of two [Au(CN)2]- anions linked to [Ni(en)2]2+ unit in trans configuration. Trinuclear units are joined by aurophilic interactions to form 1D zigzag chains. The magnetic properties of these compounds are strongly dominated by the local anisotropy of the octahedral Ni(II) ions, thus indicating that the magnetic exchange interaction mediated by dicyanoaurate bridging groups, if it exists, is very weak. To get insight into the electronic properties of the inter- and intramolecular interactions of the [Au(CN)2]- building blocks, the structures of different aggregates of dicyanogold units were optimized and then analyzed by making use of atoms-in-molecules (AIM) theory. Moreover, bond indices were calculated by methods based upon nonlinear population analysis.

Aurophilicity as a cofactor in crystal engineering. Dicyanoaurate(I) anion as a building block in a novel Co(II)-Au(I) bimetallic assembly.

A 2D grid-shaped cyanide-bridged Co(II)-Au(I) bimetallic coordination polymer, [Co(DMF)2(Au(CN)2)2], has been prepared from the [Au(CN)2]- building block; sheets associate pair-wise by aurophilic interactions and the compound exhibits zeolite-like properties.

Plasticity of Cl-Te-Cl Fragments. Synthesis, Single-Crystal X-ray, and NBO Study of (1-Thia-2-tellura-1-phenyl-4-chloro)cyclopentane 2,2,2-Trichloride.

Tellurium tetrachloride and allylphenyl sulfide react to form (1-thia-2-tellura-1-phenyl-4-chloro)cyclopentane 2,2,2-trichloride. The crystal and molecular structure were determined by single-crystal X-ray techniques. The crystals belong to the monoclinic system, space group P2(1)/c (No. 14) with a = 6.020(3) Å, b = 11.46(1) Å, c = 20.156(2) Å, beta = 97.53(2) degrees, V = 1379(1) Å(3), and Z = 4. The structure was refined to the final R value of 0.036. The coordination around Te(IV) is distorted psi octahedral with three Cl atoms in the equatorial positions. The axial Te(1)-C(1) bond opposite to the lone pair of electrons at the Te(IV) atom completes the coordination polyhedron. The intramolecular Te-S distance is 2.903(3) Å. Symmetric and asymmetric deformation modes were established to describe the plasticity of the Cl-Te-Cl fragments extracted from the Cambridge Structural Database. The hypervalency of Te(IV) manifests itself as plasticity in the equatorial plane of the coordination sphere. The NBO calculations show that all of the equatorial Te-Cl bonds are highly polarized and the electrons reside mainly on the Cl atoms.