Electronic tuning of the lability of Pt(II) complexes through π-acceptor effects.: Correlations between thermodynamic, kinetic, and theoretical parameters

pi-Acceptor effects are often used to account for the unusual high lability of (Pt(terpy)L]((2-n)+) (terpy = 2,2':6',2"-terpyridine) complexes. To gain further insight into this phenomenon, the pi-acceptor effect was varied systematically by studying the lability of [Pt(diethylenetriamine)OH2](2+) (aaa), [Pt(2,6-bis-aminomethylpyridine)OH2](2)+ (apa), [Pt(N(pyridyl-2-methyl)-1,2-diamino-ethane)OH2](2+) (aap), [Pt(bis(2-pyridylmethyl)amine)OH2](2+) (pap), [Pt(2,2'-bipyridine)(NH3)(OH2)](2+) (app), and [Pt(terpy)OH2](2+) (ppp). The crystal structure of the apa precursor [Pt(2,6-bisaminomethylpyridine)Cl].Cl-H2O was determined. The substitution of water by a series of nucleophiles, viz. thiourea, N,N-dimethylthiourea, N,N,N,N'-tetramethylthiourea, I-, and SCN-, was studied under pseudo-first-order conditions as a function of concentration, pH, temperature, and pressure, using stopped-flow techniques. The data enable an overall comparison of the substitution behavior of these complexes, emphasizing the role played by the kinetic cis and trans pi-acceptor effects. The results indicate that the cis, pi-acceptor effect is larger than the trans pi-acceptor effect, and that the pi-acceptor effects are multiplicative. DFT calculations at the B3LYP/LACVP** level of theory show that, by the addition of a-acceptor ligands to the metal, the positive charge on the metal center increases, and the energy separation of the frontier molecular orbitals (E-LUMO - E-HOMO) of the ground state Pt(II) complexes decreases. The calculations collectively support the experimentally observed additional increase in reactivity when two pi-accepting rings are adjacent to each other (app and ppp), which is ascribed to "electronic communication" between the pyridine rings. The results furthermore indicate that the pK(a) value of the platinum bound water molecule is controlled by the pi-accepting nature of the chelate system and reflects the electron density around the metal center. This in turn controls the rate of the associative substitution reaction and was analyzed using the Hammett equation.