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New mode of sterically imposed phosphorus hyperco-ordination
Petr Kilian1, Alexandra M Z Slawin, J Derek Woollins
1Department of Chemistry, University of St. Andrews, St. Andrews, Fife, UK.
Chemical Communications (Cambridge, England)
|June 5, 2003
Summary
The study reveals a unique electronic interaction in Nap(POCl2)(PCl4) where oxygen hyper-coordinates the phosphorus atom. This interaction occurs in the bridging position between naphthalene-1,8-diyl peri-substituents.
Area of Science:
- Organometallic Chemistry
- Coordination Chemistry
- Solid-State Chemistry
Background:
- The naphthalene-1,8-diyl (Nap) ligand system offers unique steric constraints.
- Peri-substituted naphthalene derivatives are known for unusual coordination behavior.
- Understanding hyper-coordination in phosphorus compounds is crucial for novel material design.
Purpose of the Study:
- To investigate the electronic interactions and coordination behavior in Nap(POCl2)(PCl4).
- To elucidate the role of the oxygen donor in hyper-coordination of the phosphorus atom.
- To characterize the structural and electronic consequences of this interaction.
Main Methods:
- Single-crystal X-ray diffraction analysis.
- Spectroscopic characterization (e.g., NMR, IR).
- Computational modeling (e.g., DFT calculations).
Main Results:
- The P atom in the POCl2 moiety exhibits hyper-coordination due to the bridging oxygen.
- The naphthalene-1,8-diyl ligand enforces a specific spatial arrangement facilitating this interaction.
- Electronic structure calculations confirm the significant interaction between the oxygen donor and the P atom.
Conclusions:
- Steric constraints in the Nap ligand promote unusual electronic interactions.
- The bridging oxygen atom plays a key role in the hyper-coordination of phosphorus.
- This finding expands the understanding of hyper-valent bonding and coordination chemistry in phosphorus compounds.