Structurally Constrained Stibenium: Metallomimetic C-Si Bond Activation.

Area of Science:

• Main-group chemistry
• Organometallic chemistry
• Catalysis

Background:

• Pnictogen chemistry, particularly antimony, is crucial for metallomimetic catalysis.
• Structurally constrained pnictogen centers offer unique reactivity.
• Main-group elements can mimic transition metals in catalytic processes.

Purpose of the Study:

• To report a novel structurally constrained stibenium cation ([1]+) supported by a pincer ligand.
• To investigate the catalytic activity of this antimony-based cation in silicon-carbon bond activation.
• To explore its potential in silane redistribution reactions.

Main Methods:

• Synthesis of a novel stibenium cation ([1]+) using a 2,6-bis(o-carborano)pyridine pincer ligand.
• Experimental studies on the activation of Si-C bonds in hydrosilanes and tetraalkylsilanes.
• Density functional theory (DFT) for mechanistic investigations.

Main Results:

• The stibenium cation [1]+ demonstrated unprecedented activation of Si-C bonds in both hydrosilanes and tetraalkylsilanes.
• [1]+ effectively catalyzed silane redistribution reactions under mild conditions.
• Mechanistic studies indicated a metallomimetic pathway involving transition metal-like steps.

Conclusions:

• The reported stibenium cation ([1]+) is a potent catalyst for silane redistribution.
• This antimony-based catalyst operates via a metallomimetic mechanism, highlighting the potential of main-group elements in catalysis.
• The findings expand the scope of main-group catalysis and offer new avenues for silicon chemistry.