Reaction of IMesPPh with RuCl₂L₂(CHPh) (L = PPh₃ and PCy₃) gave complexes with selectivity that is dependent on the metal precursor used. RuCl₂(IMesPPh)(PPh₃)(CHPh), which adopts the rare cis chloride configuration, was inactive in ring-opening metathesis of diallyl sulfide. In contrast, the PCy₃ analogue could not be isolated, and in fact led to an unusual decomposition product with two C–H activations.