Affordable Access

Publisher Website

Oxidative addition of MeI to some cyclometalated organoplatinum(II) complexes: Kinetics and mechanism

Journal of Organometallic Chemistry
Publication Date
DOI: 10.1016/j.jorganchem.2011.10.028
  • Organoplatinum
  • Cyclomatalated
  • Oxidative Addition
  • Kinetics
  • Mechanism


Abstract New cyclometalated platinum(II) complexes [PtMe(C^N)L], 1, in which C^N = deprotonated 2-phenylpyridine (ppy), benzo[ h]quinoline (bhq) or 2-( p-tolyl)pyridine (tpy) and L = PPh 3 or PMePh 2, were synthesized by the reaction of [PtMe(C^N)(SMe 2)] with 1 equiv of L. The reaction of complexes 1 with MeI gave the cyclometalated Pt(IV) complexes [PtMe 2I(C^N)L], 3. On the basis of kinetic studies, using Uv–visible spectroscopy, it was suggested that the latter oxidative addition reactions were proceeded by an S N2 mechanism. The rates of the reactions at different temperatures were measured and consistent with the proposed mechanism, large negative Δ S ‡ values were found for each reaction. Besides, rate of reactions (in CHCl 3) involving the PPh 3 complexes [PtMe(C^N)(PPh 3)], were almost 3–5 times slower than those involving the PMePh 2 complexes [PtMe(C^N)(PMePh 2)]. This was attributed to the electronic and steric effects of PPh 3 ligand as compared with that of PMePh 2 ligand which was further confirmed using density functional theory (DFT) calculations through finding approximate structures for the described complexes.

There are no comments yet on this publication. Be the first to share your thoughts.