A Bridging Peroxide Complex of Platinum(IV)

Area of Science:

• Organometallic Chemistry
• Photochemistry
• Inorganic Chemistry

Background:

• Platinum complexes are crucial in catalysis and medicine.
• Understanding platinum complex reactivity under photolytic conditions is essential.
• The formation of multinuclear platinum species is of significant interest.

Purpose of the Study:

• To synthesize and characterize a novel diplatinum(IV) complex.
• To investigate the photolysis of an allylplatinum(IV) complex in the presence of air.
• To explore the reactivity of platinum intermediates with oxygen.

Main Methods:

• Photolysis of an allylplatinum(IV) complex ([PtBr(C3H5)(4-MeC6H4)2(bipy)], 1).
• Reaction of the photolyzed intermediate with atmospheric oxygen.
• Characterization of the resulting diplatinum(IV) complex ([{PtBr(4-MeC6H4)2(bipy)}2(μ-O2)], 2).

Main Results:

• The first diplatinum(IV) complex with a single bridging peroxide ligand was successfully synthesized.
• The synthesized complex, 2, exhibits a Pt-O-O-Pt bond.
• The Pt-O-O-Pt bond distance was determined to be 1.481(3) Å.

Conclusions:

• The photolysis of allylplatinum(IV) complexes in air can lead to the formation of diplatinum(IV) species.
• The reaction likely proceeds through a platinum(III) intermediate reacting with oxygen.
• This study reports a novel synthetic route to multinuclear platinum complexes with peroxide ligands.