Versatile coordination of cyclopentadienyl-arene ligands and its role in titanium-catalyzed ethylene trimerization.
Cationic titanium(IV) complexes with ansa-(eta(5)-cyclopentadienyl,eta(6)-arene) ligands were synthesized and characterized by X-ray crystallography. The strength of the metal-arene interaction in these systems was studied by variable-temperature NMR spectroscopy. Complexes with a C(1) bridge between the cyclopentadienyl and arene moieties feature hemilabile coordination behavior of the ligand and consequently are active ethylene trimerization catalysts. Reaction of the titanium(IV) dimethyl cations with CO results in conversion to the analogous cationic titanium(II) dicarbonyl species. Metal-to-ligand backdonation in these formally low-valent complexes gives rise to a strongly bonded, partially reduced arene moiety. In contrast to the eta(6)-arene coordination mode observed for titanium, the more electron-rich vanadium(V) cations [cyclopentadienyl-arene]V(N(i)Pr(2))(NC(6)H(4)-4-Me)(+) feature eta(1)-arene binding, as determined by a crystallographic study. The three different metal-arene coordination modes that we experimentally observed model intermediates in the cycle for titanium-catalyzed ethylene trimerization. The nature of the metal-arene interaction in these systems was studied by DFT calculations.
Otten
Edwin
E
Center for Catalytic Olefin Polymerization, Stratingh Institute for Chemistry, University of Groningen, Nijenborgh 4, 9747 AG, Groningen, The Netherlands.
Batinas
Aurora A
AA
Meetsma
Auke
A
Hessen
Bart
B