Molybdenum(0) tricarbonyl and tetracarbonyl complexes with a cationic pyrazolylpyridine ligand: synthesis, crystal structures and catalytic performance in olefin epoxidation.

The synthesis of molybdenum(0) tricarbonyl and tetracarbonyl complexes of the form [Mo(CO) 3 (ptapzpy)Br] (1) and cis -[Mo(CO) 4 (ptapzpy)]Br (2) is reported, where ptapzpy = 2-(1-propyltrimethylammonium-3-pyrazolyl)pyridine. Preparation of these derivatives was accomplished either through thermal replacement of CO in Mo(CO) 6 (for 1) or substitution under milder conditions of piperidine ligands in the precursor cis -[Mo(CO) 4 (pip) 2 ] (for 2). The crystal structures of the ligand [ptapzpy]Br and complexes 1 and 2 were determined. Thermal treatment of 2 at 125-150 °C leads to mono decarbonylation and formation of 1. On the other hand, oxidative decarbonylation of 1 and 2 by reaction with tert -butylhydroperoxide (TBHP, 10 equiv.) gives a molybdenum oxide hybrid material formulated as [Mo 3 O 9 ([ptapzpy]Br) 2 ]·nH 2 O (3), which was characterised by FT-IR and Raman spectroscopy, thermogravimetric analysis, and 13 C{ 1 H} CP MAS NMR spectroscopy. Compounds 1-3 were effective (pre)catalysts for the epoxidation of cis -cyclooctene at 55 °C with aqueous H 2 O 2 or TBHP (slightly better results were obtained with the former). The characterisation of the Mo-containing solids isolated after the catalytic reaction showed that poorly soluble β-octamolybdate salts, (L) x [Mo 8 O 26 ], were formed from 1-3 with TBHP and from 1 with H 2 O 2 , while soluble oxoperoxo species were formed from 3 with H 2 O 2 . These findings helped to explain the different catalytic performances obtained.