Azole Assisted C–H Bond Activation Promoted by an Osmium-Polyhydride: Discerning between N and NH

The capacity of the hexahydride complex OsH₆(PⁱPr₃)₂ (<b>1</b>) to discern between the nitrogen atom and the NH unit in the azole assisted aryl C–H bond activation has been investigated. Complex <b>1</b> reacts with 2-phenylimidazole to give OsH₃{κ²-<i>C</i>,<i>N</i>-(C₆H₄-imidazole)}­(PⁱPr₃)₂ (<b>2</b>), which has been characterized by X-ray diffraction analysis. The structure proves the higher affinity of the metal center for the N atom in the presence of the NH unit, which remains unchanged, and reveals that in the solid state the molecules of this complex form infinite chains by means of intermolecular asymmetric 3-center bifurcated dihydrogen bonds. In solution, ¹H-DOSY NMR experiments suggest that the association degree decreases as the temperature increases. The fused six-membered ring of benzimidazole weakens the NH bond, enhancing its reactivity. As a consequence, complex <b>1</b> cannot discern between the N atom and the NH unit of 2-phenylbenzimidazole. Thus, the treatment of <b>1</b> with this substrate leads to a mixture of OsH₃{κ²-<i>C</i>,<i>N</i>-(C₆H₄-benzimidazole)}­(PⁱPr₃)₂ (<b>3</b>) and the dinuclear species (PⁱPr₃)₂H₃Os­(C₆H₄-benzimidazolate)­OsH­(η²-H₂)­(PⁱPr₃)₂ (<b>4</b>). The latter is the result of a N-assisted <i>ortho</i>-C–H bond activation of the phenyl group promoted by 0.5 equiv of <b>1</b> and the N–H bond activation promoted by the remaining 0.5 equiv of hexahydride <b>1</b> along with the agostic coordination of the remaining <i>ortho</i>-C–H bond to the metal center of the unsaturated fragment OsH­(η ²-H₂)­(PⁱPr₃)₂. The comparison of the redox properties of <b>3</b> and <b>4</b> suggests that the interaction between the metal centers in the dinuclear compound is negligible. The replacement of the NH group of the azoles by a sulfur atom does not modify the behavior of the substrates. Thus, the reactions of <b>1</b> with 2-phenylthiazole and 2-phenylbenzothiazole afford OsH₃{κ ²-<i>C</i>,<i>N</i>-(C₆H₄-thiazole)}­(PⁱPr₃)₂ (<b>5</b>) and OsH₃{κ²-<i>C</i>,<i>N</i>-(C ₆H₄-benzothiazole)}­(PⁱPr₃)₂ (<b>6</b>). In turn, complexes <b>2</b>, <b>3</b>, <b>5</b>, and <b>6</b> are phosphorescent