The Perfluoro-o-phenylene-mercury Trimer [Hg(o-C6F4)]3 - a Textbook Example of Phase-Dependent Structural Differences.

The geometric and electronic structure of [Hg(o-C6F4)]3 (1) in the gas phase, i.e. free of intermolecular interactions, was deter-mined by a synchronous gas-phase electron diffraction/mass spec-trometry experiment (GED/MS), complemented by quantum chemi-cal calculations. 1 is stable up to 498 K and the gas phase contains a single molecular form: the trimer [Hg(o-C6F4)]3. It has a planar structure of D3h sym-metry with a Hg-C distance of 2.075(5) Å and a Hg-Hg distance of 3.614(7) Å (both rh1). Structural differences between the crystalline and gaseous state have been analyzed. Different DFT functio-nal-basis combi-na-tions were tested, demon-stra-ting the importance to consider the relativistic effects of the mercury atoms. The combi-na-tion PBE0/-MWB(Hg),cc-pVTZ(C,F) turned out to be the most appro-priate for the geometry optimization of such organomercurials. The elec-tronic structure of 1, the nature of the chemical bonding in C-Hg-C fragments and the nature of the Hg···Hg inter-actions have been analyzed in terms of the Natural Bond Orbital (NBO) and Quantum Theory of Atoms in Molecules (QTAIM) approaches. The influence of the nature of halogen substi-tution on the structure of the molecules in the series [Hg(o-C6H4)]3, [Hg(o-C6F4)]3, [Hg(o-C6Cl4)]3, [Hg(o-C6Br4)]3 was also analyzed.

The Structure of Mn(acac)3 -Experimental Evidence of a Static Jahn-Teller Effect in the Gas Phase.

The structure of free manganese(III) tris(acetylacetonate) [Mn(acac)3 ] was determined by mass-spectrometrically controlled gas-phase electron diffraction. The vapor of Mn(acac)3 at 125(5) °C is composed of a single conformer of Mn(acac)3 in C2 symmetry with the central structural motif of a tetragonal elongated MnO6 octahedron and 47(2) mol % of acetylacetone (Hacac) formed by partial thermal decomposition of Mn(acac)3 . Three types of Mn-O separations have been refined (rh1 =2.157(16), 1.946(5), and 1.932(5) Å. We have found no indication for a significant deviation of the -C-C-C-O-Mn-O- six-membered rings from planarity, which is observed in the solid state.

Gas-phase structure of 1,8-bis[(trimethylsilyl)ethynyl]anthracene: cog-wheel-type vs. independent internal rotation and influence of dispersion interactions.

The gas-phase structure of 1,8-bis[(trimethylsilyl)ethynyl]anthracene (1,8-BTMSA) was determined by a combined gas electron diffraction (GED)/mass spectrometry (MS) experiment as well as by quantum-chemical calculations (QC). DFT and dispersion corrected DFT calculations (DFT-D3) predicted two slightly different structures for 1,8-BTMSA concerning the mutual orientation of the two -C-C[triple bond, length as m-dash]C-SiMe3 units: away from one another or both bent to the same side. An attempt was made to distinguish these structures by GED structural analysis. To probe the structural rigidity, a set of Born-Oppenheimer molecular dynamics (BOMD) calculations has been performed at the DFT-D level. Vibrational corrections Δr = ra - re were calculated by two BOMD approaches: a microcanonically (NVE) sampled ensemble of 20 trajectories (BOMD(NVE)) and a canonical (NVT) trajectory thermostated by the Noose-Hoover algorithm (BOMD(NVT)). In addition, the conventional approach with both, rectilinear and curvilinear approximations (SHRINK program), was also applied. Radial distribution curves obtained with models using both MD approaches provide a better description of the experimental data than those obtained using the rectilinear (SHRINK) approximation, while the curvilinear approach turned out to lead to physically inacceptable results. The electronic structure of 1,8-BTMSA was investigated in terms of an NBO analysis and was compared with that of the earlier studied 1,8-bis(phenylethynyl)anthracene. Theoretical and experimental results lead to the conclusion that the (trimethylsilyl)ethynyl (TMSE) groups in 1,8-BTMSA are neither restricted in rotation nor in bending at the temperature of the GED experiment.

1,8-Bis(phenylethynyl)anthracene - gas and solid phase structures.

1,8-Bis(phenylethynyl)anthracene (1,8-BPEA) was synthesized by a twofold Kumada cross-coupling reaction. The molecular structure of 1,8-BPEA was determined using a combination of gas-phase electron diffraction (GED), mass spectrometry (MS), quantum chemical calculations (QC) and single-crystal X-ray diffraction (XRD). Five rotamers of the molecule with different orientations of phenylethynyl groups were investigated by DFT calculations. According to these, molecules of C2 symmetry with co-directional rotation of the phenylethynyl groups are predicted to exist in the gas phase at 498 K. This was confirmed by a GED/MS experiment at this temperature. The bonding of this conformer was studied and described in terms of an NBO-analysis. Dispersion interactions in the solid state structure and in the free molecule are discussed. In the solid this symmetry is broken; the asymmetric unit of the single crystal contains 3.5 molecules and a herringbone packing motif of π-stacked dimers and trimers. The π-stacking in the dimers is between the anthracene units, and the trimers are linked by π-stacking between phenyl and anthracene units. The interaction between these stacks can be described in terms of σ(C-H)π interactions.

Topological analysis of electron densities: is the presence of an atomic interaction line in an equilibrium geometry a sufficient condition for the existence of a chemical bond?

The structure, energetics, and electron density in the inclusion complex of He in adamantane, C10H16, have been studied by density functional theory calculations at the B3LYP6-311++G(2p,2d) level. Topological analysis of the electron density shows that the He atom is connected to the four tertiary tC atoms in the cage by atomic interaction lines with (3,-1) critical points. The calculated dissociation energy of the complex He@adamantane(g)=adamantane(g) + He(g) of DeltaE=-645 kJ mol(-1) nevertheless shows that the He-tC interactions are antibonding.