Kinetics and mechanisms of inorganic and organometallic reactions of bis(amidato)-bridged cis-diammineplatinum(III) binuclear complexes: A review

“Platinum blues”-derived bis(amidato)-bridged cis-diammineplatinum(III) binuclear (dimer) complexes, head-to-head (HH) and head-to-tail (HT) [Pt₂(NH₃)₄(μ-amidato)₂(OH₂)₂]⁴⁺ (amidato = α-pyridonato, α-pyrrolidonato, or pivalamidato), react with olefins and ketones via C–H bond activation at the axial site along the Pt–Pt bond to form organoplatinum(III) dimer complexes, which react further to form oxidized and/or hydroxylated products and the corresponding platinum(II) dimer complexes. Careful kinetic investigations have been carried out by our research group to understand the reactivities of the Pt(III) dimer complexes as potential catalysts for the oxidation of organic substrates. In this review, we focus on the kinetics of inorganic and organometallic reactions of the HH and HT bis(amidato)-bridged cis-diammine Pt(III) dimer complexes with halide ions, olefins, and ketones in acidic aqueous solutions, and discuss their detailed reaction mechanisms.