Abstract
The kinetics of the forward and reverse steps of the process [Pt(NNN)Cl] + + am ⇌ [Pt(NNN)(am)] 2+ + Cl − (NNN = 2,2′ : 6′,2″-terpyridine; am = one of a number of pyridines and NH 3 covering a wide range of basicity) have been studied in methanol at 25°C. Both forward and reverse reactions obey the usual two-term rate law observed in square-planar substitution. The reactivity and the ability of the chloro-complex to discriminate among the nucleophiles, as well as the sensitivity of the rate of the chloro entry upon the nature of the displaced base and the steric factors in both the forward and reverse processes are discussed in terms of intimate mechanism and compared with data for a number of different Pt II systems. The equilibrium constants for the reactions have been determined from the ratio of the rate constants.
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