Thiophosphinoyl-Tethered Ylide-Substituted Heavier Carbenes: Synthesis, Structures and Stabilities

Area of Science:

• Organometallic Chemistry
• Main Group Chemistry
• Inorganic Synthesis

Background:

• Ylide-substituted tetrylenes are important compounds in main group chemistry.
• Understanding their structure-property relationships is crucial for developing new materials and catalysts.

Purpose of the Study:

• To synthesize and characterize novel mono- and diylide-substituted tetrylenes (E=Ge, Sn, Pb).
• To investigate the spectroscopic and structural trends of these compounds with varying tetrel elements.
• To explore the stability and reactivity of diylidyltetrylenes.

Main Methods:

• Synthesis of ylide-substituted tetrylenes using a thiophosphinoyl-tethered metallated ylide.
• Structural analysis using X-ray crystallography.
• Spectroscopic characterization including 31P{1H} NMR.

Main Results:

• Successful synthesis of ylide-substituted germylenes, stannylenes, and plumbylenes.
• Observed trends in spectroscopic (31P NMR) and structural (C-P bond length) properties with increasing atomic number of the tetrel element.
• Diylidyltetrylenes exhibit instability towards transylidation, with a defined stability trend.
• First synthesis of unsymmetrical diylidyltetrylenes (YEY') was achieved.

Conclusions:

• The study provides the first examples of ylide-substituted plumbylenes.
• Spectroscopic and structural properties are sensitive to the nature of the tetrel element.
• The S-E bond, not C-E, is most influenced by the second ylide substituent in unsymmetrical diylidyltetrylenes.