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

Abstract

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 [Mo₃O₉([ptapzpy]Br)₂]·nH₂O (3), which was characterised by FT-IR and Raman spectroscopy, thermogravimetric analysis, and ¹³C{¹H} CP MAS NMR spectroscopy. Compounds 1–3 were effective (pre)catalysts for the epoxidation of cis-cyclooctene at 55 °C with aqueous H₂O₂ 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[Mo₈O₂₆], were formed from 1–3 with TBHP and from 1 with H₂O₂, while soluble oxoperoxo species were formed from 3 with H₂O₂. These findings helped to explain the different catalytic performances obtained.