Facial-Meridional Isomerization and Reductive Elimination in [(R₂P-o-C₆H₄)₂N]PtMe₃ (R = Ph, iPr)

Area of Science:

• Organometallic Chemistry
• Platinum Chemistry
• Coordination Chemistry

Background:

• Platinum(IV) complexes are less explored than platinum(II) counterparts.
• Understanding the reactivity and structure of platinum(IV) alkyls is crucial for catalysis and materials science.

Purpose of the Study:

• To synthesize and characterize novel platinum(IV) trialkyl complexes.
• To investigate the thermal stability and decomposition pathways of these complexes.
• To report the first examples of meridional trialkylplatinum(IV) derivatives.

Main Methods:

• Synthesis of fac-[R-PNP]PtMe3 via reaction of PtMe3I with [R-PNP]Li or H[R-PNP].
• Characterization of the resulting platinum complexes.
• Thermolysis experiments in benzene to study decomposition pathways.

Main Results:

• Quantitative synthesis of fac-[R-PNP]PtMe3 (R = Ph, iPr) was achieved.
• Thermolysis of fac-[R-PNP]PtMe3 yielded mer-[R-PNP]PtMe3 and ethane.
• The mer-[R-PNP]PtMe3 complexes represent the first reported meridional trialkylplatinum(IV) compounds.

Conclusions:

• Facile synthesis of platinum(IV) trialkyl complexes is possible.
• Thermal decomposition provides a route to meridional isomers.
• Discovery of the first meridional trialkylplatinum(IV) complexes expands the known platinum chemistry landscape.