Role of cyclometalation in controlling the rates of ligand substitution at platinum(II) complexes

The rates of chloride for triphenylphosphine substitution have been measured in dichloromethane for a series of cyclometalated [Pt(N-N-C)Cl] complexes containing a number of terdentate N-N-C. anionic ligands, derived from deprotonated alkyl-, phenyl-, and benzyl-6-substituted 2,2'-bipyridines. These rates have been compared with those of the corresponding [Pt(N-N)(C)Cl] (N-N = 2,2'-bipyridine; C = CH3 or C6H5) complexes having the same set of donor atoms but less constrained arrangements of the ligands. The reactions of the cyclometalated compounds occur as a single-stage conversion from the substrate to the ionic pair [Pt(N-N-C)(PPh3)]Cl products. There is no evidence by H-1 and P-31{H-1} NMR spectroscopy for the formation of other Pt(II) species or of concurrent ring-opening processes. In contrast, ih the monoalkyl- or monoaryl-2,2'-bipyridine complexes, chloride substitution is followed by subsequent slower processes which involve the detachment of one arm of the chelated 2,2'-bipyridine, fast cis to hans isomerization of the cis-[Pt(PPh3)(2)(eta (1)-bipy)(R)](+) transient intermediate, and, eventually, the release of free bipy, yielding trans-[Pt(PPh3)(2)(R)Cl] (R = Me or Ph). All reactions are first-order with respect to complex and phosphine concentration, obeying the simple rate law k(obsd) =: k(2)[PPh3]. The values of the second-order rate constant k(2) do not seem particularly sensitive to the nature of the bonded organic moiety (alkyl or aryl), to its structure (cyclometalated or not), to the size of the ring, or to the number of alkyl substituents on it. The effects are those foreseen on the basis of an associative mode of activation. The only exception to this pattern of behavior is constituted by the complex [Pt(bipy(phi)-H)Cl] (bipy(phi) = 6-phenyl-2,2(bipyridine), which features a significant rate enhancement with respect to the analogue [Pt(bipy)(Ph)Cl] complex. The results of this work, together with those of a previous paper, Suggest that there is not a specific role of cyclometalation in controlling the reactivity, unless an in-plane aryl ring becomes part of the pi -acceptor system of the chelated 2,2'-bipyridine, behaving as a cyclometalated analogue of the nitrogen terdentate 2,2':6',2 " -terpyridine.