T-shaped Ni0 Systems Featuring Cationic Tetrylenes: Direct Observation of L/Z-type Ligand Duality,and Alkene Hydrogenation Catalysis

We report a facile synthetic method for accessing rare T-shaped Ni⁰ species, stabilised by low-coordinate cationic germylene and stannylene ligands which behave as Z-type ligands toward Ni⁰. An in-depth computational analysis indicates significant Ni^d→E^p donation (E=Ge, Sn), with essentially no E→Ni donation. The tetrylene ligand's Lewis acidity can be modulated in situ through the addition of a donor ligand, which selectively binds at the Lewis acidic tetrylene site. This switches this binding centre from a Z-type to a classical L-type ligand, with a concomitant geometry switch at Ni⁰ from T-shaped to trigonal planar. Exploring the effects of this geometry switch in catalysis, isolated T-shaped complexes 3 a – c and 4 a – c are capable of the hydrogenation of alkenes under mild conditions, whilst the closely related trigonal planar and tetrahedral Ni⁰ complexes 5 , D , and E , which feature L-type chloro- or cationic-tetrylene ligands, are inactive under these conditions. Further, addition of small amounts of N-bases to the catalytic systems involving T-shaped complexes significantly reduces turnover rates, giving evidence for the in situ modulation of ligand electronics for catalytic switching.     

Dielectric and Electrooptic Investigations in the Nematic Phase of 5-n-Pentyl-2-[4-n-nonyloxyphenyl]-1,3-dioxane

The dielectric constant and the dielectric loss of 5-n-pentyl-2-[4-n-nonyloxyphenyl]-1,3-dioxane were investigated in the region of 0.1 to 10 MHz. An isotropy temperature was detected, at which the static dielectric anisotropy Δε₀₁ = 0. Using both the Freedericksz and the DAP effect, we measured the frequency dependence of the threshold voltage U₀ and compared the results with those of the dielectric measurements. In the case of DAP effect we could find two different types of dispersions curves of U₀.