Open AccessReactivity of phosphiranes toward nucleophiles: Theoretical and experimental investigations
Author(s) -
Coote Michelle L.,
Krenske Elizabeth H.,
Maulana Ilham,
Steinbach Jörg,
Wild S. Bruce
Publication year - 2008
Publication title -
heteroatom chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.283
H-Index - 42
eISSN - 1098-1071
pISSN - 1042-7163
DOI - 10.1002/hc.20405
Subject(s) - chemistry , heteroatom , nucleophile , reactivity (psychology) , quenching (fluorescence) , computational chemistry , reaction rate constant , ethylene , kinetic energy , carbon fibers , medicinal chemistry , thermodynamics , ring (chemistry) , kinetics , organic chemistry , catalysis , fluorescence , medicine , physics , alternative medicine , materials science , pathology , quantum mechanics , composite number , composite material
The thermodynamic and kinetic parameters for the reaction of 1‐methylphosphirane with dimethylphosphide (PMe − 2 ), proceeding via attack at the ring phosphorus atom to give Me 2 P–PMe − plus ethylene, were calculated at the G3(MP2)‐RAD(+) level. The rate constant for this mechanism ( k = 1.1 × 10 13 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