Ru(II) Complexes with a Chemical and Redox-Active S₂N₂ Ligand: Structures, Electrochemistry, and Metal–Ligand Cooperativity

Here we describe the synthesis, structures, and reactivity of Ru complexes containing a triaryl, redox-active S₂N₂ ligand derived from <i>o</i>-phenylenediamine and thioanisole subunits. The coordination chemistry of <i>N</i>,<i>N′</i>-bis­[2-(methylthio)­phenyl]-1,2-diaminobenzene [H₂(^MeSNNS^Me)] was established by treating RuCl₂(PPh₃)₃ with H₂(^MeSNNS^Me) to yield {Ru­[H₂(^MeSNNS^Me)]­Cl­(PPh₃)}Cl (<b>1</b>). Coordinated H₂(^MeSNNS^Me) was sequentially deprotonated to form Ru­[H­(^MeSNNS^Me)]­Cl­(PPh₃) (<b>2</b>) followed by the five-coordinate, square pyramidal complex Ru­(^MeSNNS^Me)­(PPh₃) (<b>3</b>). Single-crystal X-ray diffraction (XRD) studies revealed that the ligand structurally rearranged around the metal at each deprotonation step to conjugate the adjacent aryl groups with the <i>o</i>-phenylenediamine backbone. Deprotonation of <b>2</b> with NaBH₄ or treatment of <b>3</b> with BH₃·tetrahydrofuran (THF) yielded Ru­[(μ-H)­BH₂]­(^MeSNNS^Me)­(PPh₃) (<b>5</b>) with BH₃ bound across a Ru–N bond in a metal–ligand cooperative fashion. The cyclic voltammogram of <b>3</b> in THF revealed three redox events consistent with one-electron oxidations and reductions of the <i>o</i>-phenylenediamine backbone and the metal (Ru³⁺/Ru²⁺). Reactions of <b>3</b> with CO, HBF₄, and benzoic acid yielded the new complexes Ru­(^MeSNNS^Me)­(CO)­(PPh₃), {Ru­[H­(^MeSNNS^Me)]­(PPh₃)­(THF)}­BF₄, and Ru­[H­(^MeSNNS^Me)]­(PPh₃)­(PhCO₂), indicating broader suitability for small molecule binding and reactivity studies. Subsequent nuclear magnetic resonance spectroscopy, infrared spectroscopy, and mass spectrometry data are reported in addition to molecular structures obtained from single-crystal XRD studies