Heavier Cyanate, Nitrile and Nitroso Analogues: New Opportunities in Synthesis

The cyanate (NCO-), cyanide (CN-) and nitrosonium (NO+) ions are stable nitrogen-containing species that serve as functional groups in organic chemistry and ligands to transition metals. They are routinely used as illustrative examples of specific chemical properties. For example, the cyanate ion is an archetypal ambidentate nucleophile, the cyanide ion an exemplary strong-field ligand, and metal nitrosyl compounds helped establish the concept of redox “non-innocent” ligands. By contrast, phosphorus-containing analogues of such species are extremely rare or were entirely unknown until recently. This talk will describe our efforts at developing the chemistry of such compounds. Specifically, we will focus on how the phosphaethynolate ion (P=C=O-; a heavier cyanate analogue), can be used to access a Grignard-like cyaphide (C P-) transfer reagent, and how such a species can be used to target multi-metallic complexes. The talk will also describe our recent attempt at accessing a phosphinidene oxide, the first example of an unsupported molecular phosphorus(III) oxide.

Speaker: Jose Goicochea, Indiana University