Trans,trans,trans-[ReO2I2(PPh3)2], a rare rhenium(VI) complex — Synthesis and DFT study

• Dioxo-diphosphine complex of rhenium(VI)
• Mild reducing agent iodide as ligand
• DFT studies
• Wave function analysis
• X-ray crystal structure

The heating of cis-[ReO2I(PPh3)2] at reflux in benzene in air led to the isolation of the rhenium(VI) complex [ReO2I2(PPh3)2] (1). The compound is centrosymmetric around the octahedrally coordinated rhenium center, and the ReO bond length of 1.797(2) Å is longer than in typical trans-dioxorhenium(V) complexes. The asymmetric ReO stretching frequency occurs at 744 cm− 1. Density functional theory has been used for the calculation of the vibrational spectrum density which confirms the experimental asymmetric ReO stretching frequency. DFT calculation within the polarizable continuum model shows that complex 1 is more stable in CH2Cl2 than in the gas phase. EPR spectroscopy confirms a single d electron in 1. The crystal structure was determined by X-ray single crystal diffraction. In addition, infra-red, redox and electronic properties are also reported.

The heating of cis-[ReO2I(PPh3)2] at reflux in benzene in air led to the isolation of the rhenium(VI) complex [ReO2I2(PPh3)2] (1). The compound is centrosymmetric around the octahedrally coordinated rhenium center, and the ReO bond length of 1.797(2) Å is longer than in typical trans-dioxorhenium(V) complexes.Figure optionsDownload as PowerPoint slide