The parent phosphinidene molecule, PH, has an electron count of six at phosphorus and a triplet ground state. This reactive intermediate is thus a phosphorus analog of methylene, CH<sub>2</sub>, and it should be remembered that phosphorus has similar electronegativity to that of carbon, with which it shares a diagonal relationship, and has thus been called “the carbon copy”. Carbenes have been stabilized famously in the singlet state by placing pi-donor substituents adjacent to the otherwise electron-deficient carbon center, creating the class of molecules now referred to as N-heterocyclic carbenes, NHCs. A similar approach can be envisioned in order to stabilize the singlet state of phosphinidenes, and this is an actively emerging area of research. Bertrand has reported on the synthesis and reactivity patterns of an isolable phosphinophosphinidene encaged by sterically demanding organic residues, and we are working on the thermal generation of transient aminophosphinidenes using a new class of anthracene-based molecular precursors. I will report on our progress directed at phosphinidene transfer to metal complexes and to unactivated olefins, as well as on our current best understanding of electronic structure and chemical bonding in these systems.

On the trail of aminophosphinidenes

254th National Meeting (2017)

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