Bimetallic Complexes with Unusual Main Group Bridging Ligands

Area of Science:

• Organometallic Chemistry
• Main Group Chemistry
• Coordination Chemistry

Background:

• Rhenium complexes with β-diketiminate (BDI) ligands are valuable synthetic platforms.
• Exploring novel bonding motifs in phosphorus and germanium chemistry is crucial for advancing inorganic synthesis.

Purpose of the Study:

• To synthesize and characterize novel mono- and bimetallic rhenium complexes.
• To investigate uncommon phosphorus and germanium bonding motifs.
• To understand the role of π-bonding in stabilizing these complexes.

Main Methods:

• Reactions involving Na[(BDI)ReCp] and (BDI)Re(≡N)(η³-Cp) with phosphorus and germanium electrophiles.
• Synthesis of bridging phosphido, chlorometallogermylene, and related complexes.
• Characterization of novel mono- and bimetallic rhenium complexes.

Main Results:

• Successful synthesis of a neutral, open-shell bridging phosphido rhenium complex.
• Isolation of a stable, unsupported chlorometallogermylene complex.
• Development of new synthetic routes to trichlorogermyl, germanium-substituted triketimine, aminometallogermylene, and heterobimetallic μ-germanido complexes.
• Formation of cationic dirhenium complexes bridged by {NEN} fragments.

Conclusions:

• The study demonstrates versatile synthetic pathways to novel phosphorus and germanium complexes.
• π-bonding interactions play a significant role in stabilizing these unique organometallic structures.
• The findings expand the scope of rhenium-based main group chemistry.