N-Donor Ligand Supported "ReO2+": A Pre-Catalyst for the Deoxydehydration of Diols and Polyols.

A selected number of tetradentate N2Py2 ligand-supported ReO2+ complexes and a monodentate pyridine-supported ReO2+ complex have been investigated as catalysts for the deoxydehydration (DODH) of diols and polyols. In situ 1H NMR experiments showed that these N-donor ligand-supported ReO2+ complexes are only the pre-catalyst of the DODH reaction. Treatment of (N2Py2) ReO2+ with an excess amount of water generates an active species for DODH catalysis; use of the Re-product of this reaction shows a much shorter induction period compared to the pristine complex. No ligand is coordinated to the "water-treated" complex indicating that the real catalyst is formed after ligand dissociation. IR analysis suggested this catalyst to be a rhenium-oxide/hydroxide oligomer. The monodentate pyridine ligand is much easier to dissociate from the metal center than a tetradentate N2Py2 ligand, which makes the Py4ReO2+-initiated DODH reaction more efficient. For the Py4ReO2+-initiated DODH of diols and biomass-based polyols, both PPh3 and 3-pentanol could be used as a reductant. Excellent olefin yields are achieved. [ABSTRACT FROM AUTHOR]