Reactions of TpRu(CO)(NCMe)(Me) (Tp = Hydridotris(pyrazolyl)borate) with Heteroaromatic Substrates: Stoichiometric and Catalytic C−H Activation

The Ru(II) complex TpRu(CO)(NCMe)(Me) (Tp = hydridotris(pyrazolyl)borate) initiates carbon−hydrogen bond activation at the 2-position of furan and thiophene to produce methane and TpRu(CO)(NCMe)(aryl) (aryl = 2-furyl or 2-thienyl). Solid-state structures have been determined for TpRu(CO)(NCMe)(2-thienyl) and [TpRu(CO)(μ-C,S-thienyl)]2. The complex TpRu(CO)(NCMe)(2-furyl) serves as a catalyst for the formation of 2-ethylfuran from ethylene and furan. DFT calculations of the C−H activation of furan by {(Tab)Ru(CO)(Me)} (Tab = tris(azo)borate) indicate that the C−H activation sequence does not proceed through a Ru(IV) oxidative addition intermediate.