The phosphaethynolate anion, PCO–, is a heavy analogue of the valence isoelectronic cyanate ion (OCN−).The phosphaethynolate anionhas opened an exciting new avenue of research in the field of organophosphorus chemistry; development over the past 8 years has demonstrated its versatility as a chemical precursor towards, for example, the synthesis of phosphorus-containing heterocycles, as a monoanionic phosphide source, and for low-valent compounds.[1b][2b]
The success of the 2-phosphaethynolate ion prompted us to explore the chemistry of its heavier analogues. The arsenic‐containing ion, AsCO−, was first isolated in 2016 by our research group, and promises to be a similarly versatile reagent in chemical synthesis, having already been employed for the synthesis of several novel molecules.[3b]
We have expanded the series further through a modular approach to the modification of the synthesis. This approach gives access to substitution at both the pnictogen and chalcogen sites, yielding a family of heavy cyanate analogues for further exploration.[4b]
[1b] J. M. Goicoechea, H. Grutzmacher, Angew. Chem. Int. Ed. 2018, 57, 16968-16994
[2b] A. R. Jupp J. M. Goicoechea, Angew. Chem. Int. Ed. 2013, 52, 10064-10067
[3b] A. Hinz, J. M. Goicoechea, Angew. Chem. Int. Ed. 2016, 55, 8536-8541
[4b] F. Tambornino, A. Hinz, R. Koppe, J. M. Goicoechea, Angew. Chem. Int. Ed. 2018, 57, 8230-8234