Competitive Aryl−Iodide vs Aryl−Aryl Reductive Elimination Reactions in Pt(IV) Complexes: Experimental and Theoretical Studies

The platinum(IV) complex trans-(dmpe)PtIV(Ar)2I2 (2, dmpe = 1,2-dimethylphosphinoethane, Ar
= 4-FC6H4) rapidly reacts, upon moderate heating in solution under ambient light, via two distinct
pathways:  isomerization to the corresponding cis-isomer (3) and Ar−I reductive elimination to give (dmpe)PtII(Ar)I (4). Complex 3 undergoes, upon prolonged heating at high temperatures, an exclusive Ar−Ar
reductive elimination reaction to give (dmpe)PtIII2. Experimental and DFT studies showed that the 2-to-3
isomerization proceeds via three pathways:  photochemical or thermal phosphine chelate opening and a
mechanism involving cleavage of the Pt−I bond. The isomerization reaction is significantly slowed down
but not stopped in the absence of light or in the presence of an excess of tetra-n-butylammonium iodide.
On the other hand, the Ar−I reductive elimination from 2 proceeds via the Ptδ+−Iδ- ion pairlike transition
state. Use of the rigid dmpe analogue 1,2-dimethylphosphinobenzene (dmpbz) as the ligand shuts down
the chelate ring-opening isomerization pathway and enables faster Ar−I reductive elimination thus making
the latter reaction the major reaction route for the dmpbz supported trans-diiodo Pt(IV) complex 8.