Triple-decker sandwich complexes with a bent cyclo-P₅ middle-deck.

Area of Science:

• Organometallic Chemistry
• Inorganic Chemistry
• Materials Science

Background:

• Triple-decker complexes are coordination compounds with three metal centers sandwiched between organic ligands.
• Phosphorus-rich ligands, such as the P5 ring, offer unique electronic and structural properties for complex formation.
• Organometallic chemistry explores compounds containing metal-carbon bonds, crucial for catalysis and materials.

Purpose of the Study:

• To synthesize and characterize novel triple-decker complexes incorporating an organo-substituted P5 middle-deck.
• To investigate the reactivity of P5 anions with various transition metal complexes.
• To explore the electronic structure of these newly synthesized organophosphorus compounds.

Main Methods:

• Synthesis of triple-decker complexes via reaction of [Cp*Fe(η⁴-P5R)]⁻ precursors with halogeno-bridged transition metal dimers ([Cp'''MX]₂).
• Oxidation of a synthesized triple-decker complex using [Cp₂Fe][PF₆] to yield a cationic complex.
• Density Functional Theory (DFT) calculations to elucidate the electronic structure of the synthesized complexes.

Main Results:

• Successful synthesis of new triple-decker complexes with organo-substituted P5 middle-decks.
• Isolation of a cationic triple-decker complex through oxidation, demonstrating tunable electronic properties.
• DFT calculations provided insights into the bonding and electronic configurations of the novel complexes.

Conclusions:

• The study expands the scope of triple-decker complex synthesis by incorporating functionalized P5 ligands.
• The successful synthesis and characterization of these complexes open avenues for exploring P5-based organometallic frameworks.
• This work contributes to the understanding of electronic structures in complex organophosphorus systems.