TY - JOUR
T1 - Reactivity of phosphiranes toward nucleophiles
T2 - Theoretical and experimental investigations
AU - Coote, Michelle L.
AU - Krenske, Elizabeth H.
AU - Maulana, Ilham
AU - Steinbach, Jörg
AU - Wild, S. Bruce
PY - 2008/3
Y1 - 2008/3
N2 - The thermodynamic and kinetic parameters for the reaction of 1-methylphosphirane with dimethylphosphide (PMe2-), 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 × 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.
AB - The thermodynamic and kinetic parameters for the reaction of 1-methylphosphirane with dimethylphosphide (PMe2-), 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 × 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.
UR - http://www.scopus.com/inward/record.url?scp=40749154881&partnerID=8YFLogxK
U2 - 10.1002/hc.20405
DO - 10.1002/hc.20405
M3 - Article
AN - SCOPUS:40749154881
SN - 1042-7163
VL - 19
SP - 178
EP - 181
JO - Heteroatom Chemistry
JF - Heteroatom Chemistry
IS - 2
ER -