Exploring Singlet Carbyne Anions and Related Low-Valent Carbon Species Utilizing a Cyclic Phosphino Substituent

Abstract

The advancement of synthetic methodologies is fundamentally driven by a deeper understanding of the structure–reactivity relationships of reactive key intermediates. Carbyne anions are compounds featuring a monovalent anionic carbon possessing four nonbonding valence electrons, which were historically confined to theoretical constructs or observed solely within the environment of gas-phase studies. These species possess potential for applications across diverse domains of synthetic chemistry and ancillary fields. This Account details our focused efforts to isolate singlet carbyne anions and explores our isolation of a range of related low-valent carbon species. Our achievements include the synthesis and characterization, under normal laboratory conditions, of gold-substituted free carbenes, copper carbyne anion complexes, ketenyl anions, keteniminyl anions, and a free stannyne. These have been accomplished using a bulky cyclic phosphino substituent, which effectively stabilizes these reactive species.

Our journey commenced with the isolation of gold-substituted phosphinocarbenes, characterized by a robust carbon–gold covalent single bond, and progressed to the isolation of copper carbyne anion complexes featuring a carbon–copper ionic bond. This was realized through the synergistic combination of a bulky cyclic phosphino group and a closed-shell electron-rich late transition metal. The robustness of the carbon–gold bond contrasts markedly with the susceptibility of the carbon–copper bond, which imparts to the copper complexes the behavior characteristic of a phosphinocarbyne anion within the coordination sphere of copper, thereby enabling unique carbyne anion transfer reactions. The tri-active ambiphilic nature of the anionic carbon in these copper carbyne complexes enables the formation of three chemical bonds at the carbon center through one-pot reactions. Subsequent investigations unveiled ligand exchange reactions at the carbyne anion site, leading to the generation of stable crystalline ketenyl and keteniminyl anions. These species emerge as potent synthons capable of producing a diverse array of derivatives. In addition, we isolated a free phosphinostannyne, a rare species featuring a carbon–tin multiple bond and two adjacent ambiphilic centers. Collectively, these compounds have demonstrated a remarkable propensity for engaging in a spectrum of unique reactions, underscoring their versatility and confirming their utility in synthesizing uncharted, unique main group species.

The methodologies and insights derived from our research contribute to the broader understanding of low-valent carbon species and may provide a platform for future innovations in synthetic chemistry, catalytic processes, and novel materials. As we continue to explore and develop this area of study, we hope that these low-valent carbon species might follow in the footsteps of stable singlet carbenes, potentially finding applications across various fields in the future.