Formation kinetics of the metal-metal bonded binuclear [(CN)(5)Pt-TI(CN)](-) (1) and the trinuclear [(CN)(5)Pt-TI-Pt(CN)(5)](3-) (2) complexes is studied, using the standard mix-and-measure spectrophotometric method. The overall reactions are Pt(CN)(4)(2-) + TI(CN)(2)(+) z = 1 and Pt(CN)(4)(2-) + [(CN)(5)Pt-TI(CN)](-) = 2. The corresponding expressions for the pseudo-first-order rate constants are k(obs) = (k(1)[TI(CN)(2)(+)] + k(-1))[TI(CN)(2)(+)] (at TI(CN)(2)(+) excess) and k(obs) = (k(2b)[Pt(CN)(4)(2-)] + k(-2b))[HCN] (at Pt(CN)(4)(2-) excess), and the computed parameters are k(1) 1.04 +/-0.02 M-2 s(-1), k(-1) = k(1)/K-1 = 7 x 10(-5) M-1 s(-1) and k(2b) = 0.45 +/- 0.04 M-2 s(-1), K-2b = 26 +/-6 M-1, k(-2b) = k(2b)/K-2b = 0.017 M-1 s(-1), respectively. Detailed kinetic models are proposed to rationalize the rate laws. Two important steps need to occur during the complex formation in both cases: (i) metal-metal bond formation and (ii) the coordination of the fifth cyanide to the platinum site in a nucleophilic addition. The main difference in the formation kinetics of the complexes is the nature of the cyanide donor in step ii. In the formation of [(CN)5Pt-TI(CN)]-, TI(CN)2+ is the source of the cyanide ligand, while HCN is the cyanide donating agent in the formation of the trinuclear species. The combination of the results with previous data predict the following reactivity order for the nucleophilic agents: CN- > TI(CN)(2)(+) > HCN.