The abnormally bound, anionic NHC-borane complex [Ru(IDipp-BF3)(p-cymene)Cl](2) (4; IDipp-BF3=1,3-(2,6-iPr(2)C(6)H(3))(2)-2-BF3(C3HN2)-4-yl) was synthesized by transmetalation from Li[(IDipp-BF3)(2)Ag]. Addition of donors gave species of the form [Ru(IDipp-BF3)(p-cymene)(L)Cl], whereas halide abstraction with Ag(Et2O)[B(C6F5)(4)] gave CH activation of the methine position of the IDippBF(3) ligand.