No abstract

The one-electron oxidations of 1,8-chalcogen naphthalenes Nap(SPh)2 (1) and Nap(SPh)(SePh) (2) lead to the formation of persistent radical cations 1(•+) and 2(•+) in solution. EPR spectra, UV-vis absorptions, and DFT calculations show a three-electron σ-bond in both cations. The former cation remains stable in the solid state, while the latter dimerizes upon crystallization and returns to being radical cations upon dissolution. This work provides conclusive structural evidence of a sulfur-sulfur three-electron σ-bond (in 1(•+)) and a rare example of a persistent heteroatomic three-electron σ-bond (in 2(•+)).

A series of vanadium(V) complexes bearing tetradentate amine trihydroxy ligands [NOOO], which differ in the steric and electronic properties, have been synthesized and characterized. Single crystal X-ray analysis showed that these complexes are five or six coordinated around the vanadium center in the solid state. Their coordination geometries are octahedral or trigonal bipyramidal. In the presence of Et 2 AlCl, these complexes have been investigated as the efficient catalysts for ethylene polymerization and ethylene/norbornene copolymerization at elevated reaction temperature and produced the polymers with unimodal molecular weight distributions (MWDs), indicating the single site behaviors of these catalysts. Both the steric hindrance and electronic effect of the groups on the tetradentate ligands directly influenced catalytic activity and the molecular weights of the resultant (co)poly-mers. Other reaction parameters that influenced the polymerization behavior, such as reaction temperature, ethylene pressure, and comonomer concentration, are also examined in detail. Furthermore, high catalytic activities of up to 3.30 kg polymer/mmol V Áh were also observed when these complexes were applied to catalyze the copolymerization of ethylene and 5-norbornene-2-methanol, producing the high-molecularweight copolymers (M w ¼ 157-400 kg/mol) with unimodal MWDs (M w /M n ¼ 2.5-3.0) and high polar comonomer incorporations (up to 12.3 mol %).

Three-electron s-bonding that was proposed by Linus Pauling in 1931 has been recognized as important in intermediates encountered in many areas. A number of three-electron bonding systems have been spectroscopically investigated in the gas phase, solution and solid matrix. However, X-ray diffraction studies have only been possible on simple noble gas dimer Xe'Xe and cyclic framework-constrained N'N radical cations. Here, we show that a diselena species modified with a naphthalene scaffold can undergo one-electron oxidation using a large and weakly coordinating anion, to afford a room-temperature-stable radical cation containing a Se'Se three-electron s-bond. When a small anion is used, a reversible dimerization with phase and marked colour changes is observed: radical cation in solution (blue) but diamagnetic dimer in the solid state (brown). These findings suggest that more examples of three-electron s-bonds may be stabilized and isolated by using naphthalene scaffolds together with large and weakly coordinating anions.