The approach to 4d/4f-polyphosphides.

Area of Science:

• Organometallic Chemistry
• Inorganic Chemistry
• Materials Science

Background:

• Divalent metallocenes of lanthanides (Ln = Sm, Yb) are reactive precursors.
• Phosphorus allotropes and their complexes offer diverse chemical properties.
• Synthesis of novel polyphosphide structures remains an active research area.

Purpose of the Study:

• To synthesize and characterize the first 4d/4f polyphosphides.
• To explore the reactivity of divalent metallocenes with phosphorus clusters.
• To investigate new P-P bond formations and phosphorus scaffold aggregations.

Main Methods:

• Reaction of divalent metallocenes [Cp*2Ln(thf)2] (Ln = Sm, Yb) with phosphorus precursors [{CpMo(CO)2}2(μ,η2:2-P2)] or [Cp*Mo(CO)2(η3-P3)].
• Isolation and characterization of resulting polyphosphide complexes using spectroscopic and crystallographic techniques.
• Analysis of reaction pathways involving reduction and rearrangement of phosphorus units.

Main Results:

• Synthesis of 16-membered bicyclic compounds [(Cp2*Ln)2P2(CpMo(CO)2)4] (Ln = Sm, Yb).
• Formation of cyclic P4 and P5 complexes, [(Cp*2Sm)2P4(CpMo(CO)2)2] and [(Cp*2Sm)3P5(CpMo(CO)2)3], from samarocene reactions.
• Obtained 4d/4f hexaphosphides [(Cp*2Ln)2P6(Cp*Mo(CO)2)2] (Ln = Sm, Yb) via reductive dimerization.

Conclusions:

• The study successfully synthesized unprecedented 4d/4f polyphosphides.
• Reactions demonstrate the ability of metallocenes to template complex phosphorus architectures.
• New P-P bond formations lead to novel phosphorus aggregations and structures.