ABSTRACT The development of phosphorus‐containing building blocks is crucial for efficient synthetic protocols in main group element chemistry. Among those, the PCN unit is a key structural motif for the construction of functional molecular frameworks. While anionic PCN‐containing species are well‐established, the isolation and utilization of neutral PCN molecules remain challenging. Herein, we report a straightforward synthesis of the neutral (cyano)phosphinidene adduct, Me 3 P─PCN, via the simple reaction of phosphorus tricyanide with trimethylphosphine. This methodology is general for a series of trialkylphosphines, yielding stable adducts R 3 P─PCN (R = Et, n Bu, Cy, t Bu). Comprehensive spectroscopic, structural, and computational studies of adduct Me 3 P─PCN confirm a polarized electron‐sharing P─P bond, with electron density shifted toward the Me 3 P moiety. Enabled by facile P─P bond cleavage, Me 3 P─PCN acts as an efficient and versatile PCN transfer reagent, providing access to diverse molecular architectures and opening new avenues for the integration of the PCN unit into complex systems.
Zhang et al. (Fri,) studied this question.