2-tert-Butyl-6-(4-fluorophenyl)pyridine reacts with K(2)PtCl(4) via the activation of an sp(2) C-H bond to give a cyclometalated complex that contains a bifurcated agostic interaction. Rearrangement of this complex results in the activation of an sp(3) C-H bond, and reaction eventually leads to a doubly cyclometalated complex where both sp(2) and sp(3) C-H bonds have been activated. Deuterium exchange studies show that a delicate balance exists between the two cyclometalations.