Reactivity of phosphiranes toward nucleophiles: Theoretical and experimental investigations

The thermodynamic and kinetic parameters for the reaction of 1‐methylphosphirane with dimethylphosphide (PMe), proceeding via attack at the ring phosphorus atom to give Me₂P–PMe⁻ plus ethylene, were calculated at the G3(MP2)‐RAD(+) level. The rate constant for this mechanism (k = 1.1 × 10¹³ L mol⁻¹ s⁻¹ at 25°C) is seven orders of magnitude greater than that for the previously studied mechanism involving attack at carbon. Experimental investigations with 1‐phenylphosphirane gave consistent results: Treatment with LiPMePh yielded no detectable polymer, and quenching with MeI gave the known diphosphine (R*, R*)‐(±)/(R*, S*)‐MePhP‐‐PMePh. © 2008 Wiley Periodicals, Inc. Heteroatom Chem 19:178–181, 2008; Published online in Wiley InterScience ( www.interscience.wiley.com ). DOI 10.1002/hc.20405