Inverting Pt-I Bond Polarization to Generate Iodonium Character

Tuning metal-ligand cooperativity to effect monodentateligand charge has not been widely studied outside of metal hydrides.Here, we explore how metal coordination sphere can be manipulatedto invert the polarization of Pt-I bonds and generate electrophilicbehavior at I. Coordinative unsaturation trans to I is key to invertingthe natural Pt-I bond polarization and is utilized to enablethe electrophilic behavior of I in cationic platinum iodide complexes.The synthesis and characterization of the iodination products of reactingbiscyclometalated arylpyridines (Pt(phpy)(2)) with I-2 and R3PI+ are reported. Abstractingiodide from Pt(phpy)(2)I-2 yields a putative 5-coordinatePt intermediate capable of transferring iodonium to a bulky phosphine.These experimental results are further assessed through charge calculationsand energy decomposition analysis (EDA).