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Updated: Jul 21, 2025

Preparation and Use of Carbonyl-decorated Carbenes in the Activation of White Phosphorus
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An Improved Synthesis of PN-adamantanoid Cages P4 (NR)6 and a Mechanistic Study of their Fourfold Oxidation
Michael A Land1, Jincheng Ren1, Nicholas J Roberts1
1Department of Chemistry, Dalhousie University, 6274 Coburg Road, Halifax, NS, B3H 4R2, Canada.
Abstract:
Phosphorus-nitrogen (PN) adamantanoid cages are valuable precursors for materials chemistry, but their syntheses are based on harsh methods that sometimes require access to restricted reagents. We report a new and scalable synthesis of PN adamantanoid compounds by chlorosilane elimination between bis-silylated amines and phosphorus trichloride. We further study the mechanism of the recently-reported four-fold oxidation of such cages with Me3 SiN3 to yield tetravalent tetrahedral connectors for materials chemistry. Reaction monitoring and kinetic modelling revealed the key rate-limiting step, but attempts to accelerate this using Lewis acid additives were unsuccessful. Nevertheless, a new four-fold oxidized PN-adamantanoid cage has been prepared and structurally characterized.
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