Nachweis von π → σ-Umlagerungen bei Ligandenverdrängungsreaktionen von π-Allyl-π-cyclopentadienyl-Palladiumkomplexen

It has been proved by NMR. measurements at low temperatures that the ligand displacement reactions of (π-all)Pd(π-C₅H₅) and Lewis bases L yielding PdL₄ proceed by a π → σ rearrangement of the allylic group as the primary step. The organic reaction product is the 1-isomer of the corresponding allylcyclopentadiene but in the reactions of (π-1,1,2-Me₃C₃H₂)Pd(π-C₅H₅) with L besides the isomeric allylcyclopentadienes also 2,3-dimethylbutadiene and cyclopentadiene are formed. The reaction mechanism will be discussed.     

Structural evidence for Pπ-Pπ conjugation in aminosubstituted phosphaalkynes

The molecular structure of 2,2,6,6-tetramethylpiperidinophosphaalkyne was determined by the X-ray structural method. The main geometrical parameters are as follows: PC 1.559(2), N C(sp) 1.316(2) Å, PC N 178.9(1)°, with an almost planar trigonal bond configuration for the N atom and the chair conformation of the piperidine ring. Structural evidence for the nitrogen lone pair conjugation with the π-system of the triple bond was found to be different in phosphaalkynes PC-NR₂ and nitriles NC NR₂. Quantum-chemical ab initio calculations (HF/631G*) showed that this is caused by a different character of polarization of the PC and NC triple bonds.     

Approaches for interpreting π electronic states and π electronic transitions

Scope and limitations of different approaches which enable π electronic systems of topologically equivalent structures to be compared have been examined. Particular attention has been paid to analyses in terms of molecular subsystems.     

Enhanced Aerogen–π Interaction by a Cation–π Force

The interaction between a noble gas atom and an aromatic π‐electron system, which mainly originates from the London dispersion force, is very weak and has not attracted enough attention yet. Herein, we reported a type of notably enhanced aerogen–π interaction between cation–π systems and noble gas atoms. The binding strength of a divalent cation–π system with a xenon atom is comparable to a moderate hydrogen bond (up to ca. 7 kcal mol^?1), whereas krypton and argon atoms produce slightly weaker interactions. Energy‐decomposition analysis reveals that the induction interaction is responsible for the stabilization of divalent cation–π?Xe species besides the dispersion interaction. Our results might be helpful to increase the understanding of some unsolved mysteries of aerogens.