Organometallic Chemistry of Platinum Complexes

Summary

The organometallic chemistry of platinum complexes encompasses a rich interplay between metal-centred electronic structure and ligand design, yielding species of profound significance in catalysis, materials science and medicinal chemistry. Platinum(II) complexes, typically adopting square-planar geometries, have long served as paradigms for fundamental studies of bond activation processes, including oxidative addition, reductive elimination and migratory insertion. The introduction of strongly donating, sterically demanding ligands has enabled fine control over reaction pathways, enhancing selectivity in cross-coupling and C–H functionalisation. In parallel, platinum(IV) species, which commonly feature octahedral coordination, provide versatile platforms for multi-step redox sequences and serve as pro-drugs in anticancer therapies. Recent efforts have focused on the rational design of ligand frameworks to modulate both steric environment and electronic density at the metal centre. Advances in cyclometalation — the formation of a metal–carbon bond via intramolecular C–H activation — have unlocked new routes to robust complexes with tailored photophysical and catalytic properties. Furthermore, quantitative measures of steric encumbrance, such as Tolman cone angles and buried volumes, have become routine tools for correlating ligand architecture with observed reactivity. Altogether, modern studies continue to expand the frontiers of platinum organometallic chemistry by integrating precise ligand engineering with mechanistic insight into bond-making and bond-breaking events.

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Organometallic Chemistry of Platinum Complexes publication trend

The graph below shows the total number of articles in organometallic chemistry of platinum complexes across all publications each year (not limited to Nature Index journals).

Technical terms

Organometallic complex: A compound containing a direct metal–carbon bond.

Cyclometalation: Intramolecular activation of a C–H bond to form a metallacyclic ring.

Trans influence: The ability of a ligand to weaken the bond opposite to it in a coordination complex.

Tolman cone angle: A quantitative measure of ligand steric bulk around a metal centre.

Buried volume: The fraction of a coordination sphere occupied by a ligand, used to assess steric demand.

References

  1. New Phosphonite Ligands with High Steric Demand and Low Basicity: Synthesis, Structural Properties and Cyclometalated Complexes of Pt(II). Inorganics (2022).
  2. Bromido[(1,2,5,6-η)-cyclo­octa-1,5-diene]methyl­platinum(II). Acta Crystallographica Section E: Crystallographic Communications (2009).
  3. (5,5′-Dimethyl-2,2′-bipyridine)­iodido­trimethyl­platinum(IV). Acta Crystallographica Section E: Crystallographic Communications (2011).

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