Computational Studies of Phosphorus-Containing Complexes

Computational studies of phosphorus‐containing complexes have become integral to the design and understanding of catalysts, materials and biologically active molecules. Advanced quantum-chemical methods, from density functional theory to high-level post-Hartree–Fock techniques, enable detailed characterisation of bonding motifs, reaction pathways and electronic structures. Investigations of low-coordinate phosphorus species have revealed the nature of P=C, P–O and P–C interactions, while analyses of ring strain energies elucidate stability trends in cyclic phosphacycles. Simulations further predict reactivity in phosphine ligand frameworks for homogeneous catalysis, guiding the synthesis of novel complexes with tailored electronic and steric properties. In materials science, modelling of phosphorus heterocycles informs the development of flame-retardant polymers and energy-storage media. Across bioinorganic contexts, computational insights into phosphate-binding sites underpin the rational design of metalloenzymes and inhibitors. By linking theoretical predictions with experimental observables such as spectroscopic signatures and thermochemical data, these studies provide a robust platform for accelerating discovery and refining mechanistic hypotheses in phosphorus chemistry.

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Computational Studies of Phosphorus-Containing Complexes publication trend

The graph below shows the total number of articles in computational studies of phosphorus-containing complexes across all publications each year (not limited to Nature Index journals).

Technical terms

Density functional theory (DFT): Quantum mechanical method modelling electron density to predict molecular properties.

Coupled-cluster (CCSD(T)): Post-Hartree–Fock technique providing highly accurate correlation energies.

Ring strain energy (RSE): Excess energy in cyclic compounds due to deviations from ideal bond angles.

Homodesmotic reaction: Balanced hypothetical reaction conserving bond types and hybridisation to compute RSE.

Wiberg bond index (WBI): Quantitative measure of bond order derived from electron density matrices.

Dewar–Chatt–Duncanson model: Framework describing σ-donation and π-backbonding in metal–ligand interactions.

References

1. Quantum Chemical Calculations on CHOP Derivatives—Spanning the Chemical Space of Phosphinidenes, Phosphaketenes, Oxaphosphirenes, and COP− Isomers. Molecules (2018).
2. Accurate Ring Strain Energies of Unsaturated Three-Membered Heterocycles with One Group 13–16 Element. Inorganic Chemistry (2022).
3. Ring Strain Energies of Three-Membered Homoatomic Inorganic Rings El3 and Diheterotetreliranes El2Tt (Tt = C, Si, Ge): Accurate versus Additive Approaches. Inorganic Chemistry (2022).