Novel rhenium(III) complexes with 5,6-diphenyl-3-(2-pyridyl)-1,2,4-trazine: X-ray structures and DFT calculations for [ReCl3(OPPh3)(dppt)] and [ReCl3(PPh3)(dppt)] complexes

The reaction of [ReOCl3(PPh3)2] with 5,6-diphenyl-3-(2-pyridyl)-1,2,4-trazine (dppt) has been examined and [ReCl3(OPPh3)(dppt)] has been obtained. The triphenylphosphine oxide can be easily replaced by PPh3 in the reaction of [ReCl3(OPPh3)(dppt)] with an excess of triphenylphosphine. The [ReCl3(OPPh3)(dppt)] and [ReCl3(PPh3)(dppt)] complexes have been structurally and spectroscopically characterized. Their molecular orbital diagrams have been calculated with the density functional theory (DFT) method, and their electronic spectra have been discussed on the basis of time-dependent DFT calculations. The compound [ReCl3(OPPh3)(dppt)] has been studied additionally by magnetic measurement. The magnetic behavior is characteristic of mononuclear complexes with d4 low-spin octahedral Re(III) complexes (3T1g ground state) and arise because of the large spin–orbit coupling (ζ = 2500 cm−1), which gives diamagnetic ground state.

Graphical abstractThe reaction of [ReOCl3(PPh3)2] with 5,6-diphenyl-3-(2-pyridyl)-1,2,4-trazine (dppt) has been examined and [ReCl3(OPPh3)(dppt)] has been obtained. The triphenylphosphine oxide can be easily replaced by PPh3 in the reaction of [ReCl3(OPPh3)(dppt)] with an excess of triphenylphosphine. The [ReCl3(OPPh3)(dppt)] and [ReCl3(PPh3)(dppt)] complexes have been structurally and spectroscopically characterized. Their molecular orbital diagrams have been calculated with the density functional theory (DFT) method, and their electronic spectra have been discussed on the basis of time-dependent DFT calculations. The compound [ReCl3(OPPh3)(dppt)] has been studied additionally by magnetic measurement.Figure optionsDownload full-size imageDownload as PowerPoint slide