Recently, there has been a growing interest in the chemistry of low-coordinate subvalent bismuth compounds. Earlier this year our group synthesized the first carbene-bismuthinidene complex by reducing cyclic(alkyl)(amino) carbene (CAAC)-Bi(III)PhCl2 to (CAAC)-Bi(I)Ph using a molecular beryllium(0) complex as a reducing agent. Since then, we have begun to explore the reactivity of our carbene-bismuth halide complexes with other highly reducing main group synthons. The reaction of sodium 2-phosphaethynolate, Na[OCP], with a small N-heterocyclic carbene supported (NHC)Bi(III)Ph2Cl produces an NHC–phosphaketene adduct (Ph2Bi(III)–P(NHC)CO). Indeed, upon the reaction with Na[OCP], the NHC ligand transferred from the Bi(III) metal center to the phosphaketene carbon atom. For comparison, Na[OCP] was reacted with (NHC)Sb(III)Ph2Cl to produce the isostructural antimony analogue, Ph2Sb(III)–P(NHC)CO. Notably, both of these NHC–phosphakene adducts undergo thermal reduction when heated to yield either tetraphenyldibismuthine (Ph2Bi(II)–Bi(II)Ph2), or tetraphenyldistibine (Ph2Sb(II)–Sb(II)Ph2).

Low coordinate antimony and bismuth complexes: Carbene transfer and thermal reduction from M(III) to M(II)

Macromolecular Chemistry: The Second Century

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ACS Spring 2020 National Meeting & Expo

The official archive and repository for all ACS Meetings & Expositions abstracts and select posters or presentations.