Tin and Lead Phosphanido Complexes: Reactivity with Chalcogens

Area of Science:

• Organometallic Chemistry
• Main Group Chemistry
• Coordination Chemistry

Background:

• The study investigates the reactivity of tin (Sn) and lead (Pb) phosphanido complexes.
• Phosphanido complexes are versatile ligands in organometallic chemistry.
• Understanding their reactions with chalcogens is crucial for developing new materials and catalysts.

Purpose of the Study:

• To explore the reactivity of tin and lead phosphanido complexes with sulfur and selenium.
• To characterize the products formed from these reactions.
• To investigate the structural differences between solution and solid-state species.

Main Methods:

• Synthesis of tin and lead phosphanido complexes.
• Reaction of complexes with sulfur and selenium.
• Characterization of products using multinuclear solution and solid-state NMR spectroscopy.

Main Results:

• Addition of sulfur to [(BDI)MPCy2] (M = Sn, Pb) consistently yielded phosphinodithioates.
• Addition of selenium to [(BDI)MPCy2] initially formed phosphinoselenoites, which could be further reacted to phosphinodiselenates.
• Reaction of [(BDI)SnP(SiMe3)2] with selenium resulted in a heavy ether, [(BDI)SnSeSiMe3].
• NMR spectroscopy revealed differences in solution and solid-state structures of tin phosphinoselenoite and phosphinodiselenoate complexes.

Conclusions:

• The reactivity of tin and lead phosphanido complexes with chalcogens is dependent on the specific chalcogen and the phosphanido ligand.
• Selenium insertion into tin and lead phosphanido complexes can lead to diverse products.
• NMR spectroscopy is a powerful tool for distinguishing between different structural forms in solution and solid-state.