New phospholyl complexes of groups 4 and 6: Syntheses, characterisation and polymerisation studies

[M(P3C2tBu2)(CO)3I] (M = Mo, 1, W, 2) have been synthesised and reacted with PCl5 for oxidation study purposes. Compounds Ti(P3C2tBu2)(Ind)Cl2], 3, and [Zr(P3C2tBu2)(Cp)Cl2], 4, were detected spectroscopically, but showed to be too unstable to be isolated. A Ti(IV) complex, [Ti(P3C2tBu2)Cl3], 5, has been formed from the reaction of [TiCl4] with the base-free ligand K(P3C2tBu2), while the Ti(III) species, [Ti(P3C2tBu2) Cl2(THF)], 6, was prepared from [TiCl3(THF)3]. Compounds 5 and 6 were studied as ethylene catalyst precursors after activation with MAO. In the studied conditions, complex 5 is the most active one with an activity of 2.2 × 105 g(molTi [E] h)−1, one order of magnitude higher than compound 6. The produced polymer is linear polyethylene.

Triphospholyl complexes of Groups 6 and 4 with the general formula [M(P3C2tBu2)(CO)3I (M = Mo, W) and [Ti(P3C2Bu2)Cl2D] (D = Cl, THF), respectively, were prepared and characterised. Some examples are shown in the figure. The Ti(III) and Ti(IV) compounds were studied as ethylene catalyst precursors after activation with MAO. [Ti(P3C2tBu2)Cl3] showed to be four times more active than its cyclopentadienyl analogue.Figure optionsDownload as PowerPoint slide