Theoretical studies on the reaction mechanisms of the oxidation of tetramethylethylene using MOCl (M=Mn, Tc and Re).

A theoretical study on the reaction mechanisms of the addition of transition metal oxo complexes of the type MOCl (M = Mn, Tc, and Re) to tetramethylethylene (TME) is presented. Theoretical calculations using B3LYP/LACVP* and M06/LACVP* (LACVP* is a combination of the 6-31G(d) basis set along with LANL2DZ pseudopotentials on the metallic centres) were performed and the results are discussed within the framework of reaction energetics. The nature of the stability of the reaction mechanisms was equivalent for both theories.

A DFT study on the reaction mechanisms of the oxidation of ethylene mediated by technetium and manganese oxo complexes.

The oxidation of ethylene catalyzed by manganese and technetium oxo complexes of the type MOL (M = Tc, Mn, and L = O, Cl, F, OH, Br, I) on both singlet and triplet potential energy surfaces (PESs) have been studied. All molecular structures were stable on the singlet PES except for the formation of the dioxylate intermediate for the MnOL (L = O, Cl, F, OH, Br, I) catalyzed pathway. Frontier molecular orbital calculations showed that electrons flow from the HOMO of ethylene into the LUMO of the metal-oxo complex for all complexes studied except for MOL (M = Tc, Mn, and L = O) where the vice versa occurs.

Effects of electrochemical properties of ferrocenylpyrazolylnickel(ii) and palladium(ii) compounds on their catalytic activities in ethylene oligomerisation reactions.

Palladium complexes of ferrocenylpyrazolylpyridine and ferrocenylpyrazolylamine were synthesised and screened as pre-catalysts (1-4) for olefin polymerisation. The pre-catalysts 1-4 on activation with EtAlCl in the presence of ethylene with chlorobenzene or hexane as solvent were highly active with 1 being the most active, with an activity of 360 kg mol Pd h. The major product from the reaction was 1-butene and high carbon content oligomers.

(3,5-Di-tert-butyl-2-eth-oxy-benzyl-idene)[2-(3,5-di-tert-butyl-1H-pyrazol-1-yl)eth-yl]amine.

The angles within the benzene ring in the title compound, C(30)H(49)N(3)O, ranging from 116.34 (16) to 124.18 (16)°, reflect the presence of electron-donating and electron-withdrawing substituents.

Intramolecular hydrogen bonding in dichloridobis(3,5-di-tert-butyl-1H-pyrazole-κN2)cobalt(II) as a consequence of ligand steric bulk.

The title compound, [CoCl(2)(C(11)H(20)ClN(2))(2)], forms two intramolecular hydrogen bonds [graph set S(5)] between the N atoms of the pyrazole ligands and the chloride ligands. This hydrogen-bonding motif is uncommon among related compounds but occurs here because of the bulk of tert-butyl substituents on the pyrazole ligands which shield the central metal atom to a significantly larger extent than pyrazole ligands with smaller 3,5-substituents.

Constructor graph description of the hydrogen-bonding supramolecular assembly in two ionic compounds: 2-(pyrazol-1-yl)ethylammonium chloride and diaquadichloridobis(2-hydroxyethylammonium)cobalt(II) dichloride.

Covalent bond tables are used to generate hydrogen-bond pattern designator symbols for the crystallographically characterized title compounds. 2-(Pyrazol-1-yl)ethylammonium chloride, C(5)H(10)N(3)(+).Cl(-), (I), has three unique, strong, charge-assisted hydrogen bonds of the types N-H.