Sterically encumbered tin and phosphorus peri-substituted acenaphthenes

Area of Science:

• Organometallic Chemistry
• Supramolecular Chemistry
• Materials Science

Background:

• Peri-substituted acenaphthenes offer a unique scaffold for exploring steric interactions.
• Understanding non-bonded interactions is crucial for designing novel molecular architectures.

Purpose of the Study:

• To synthesize and characterize novel sterically encumbered peri-substituted acenaphthenes containing tin and phosphorus moieties.
• To investigate the impact of bulky substituents on peri-distances and intramolecular interactions.
• To explore the coordination chemistry of these ligands with metal centers.

Main Methods:

• Synthesis of bis(stannane) and bis(phosphine) derivatives of acenaphthene.
• Treatment with sulfur to form bis(sulfides).
• Characterization using NMR spectroscopy, mass spectrometry, and X-ray crystallography.
• Preparation and characterization of platinum and molybdenum metal complexes.

Main Results:

• Bis(stannane) compounds show large peri-distances due to repulsive Sn-Sn interactions.
• Bis(phosphine) compounds exhibit a potential donor-acceptor interaction with short P-P distances.
• Bis(sulfides) display exceptionally long P-P separations, among the largest reported.
• Metal complexes demonstrate ligand distortion, with bis(phosphine) showing less distortion than bis(sulfide).

Conclusions:

• Steric hindrance in peri-substituted acenaphthenes significantly influences molecular geometry and non-bonded interactions.
• The P-P interaction in bis(phosphines) and the large P-P distances in bis(sulfides) highlight the versatility of this scaffold.
• The synthesized ligands can coordinate to metal centers, forming complexes with distorted geometries.