
TY  - JOUR
A1  - Schiesser, CH 
A1  - Wild, LM 
T1  - Homolytic Substitution at Phosphorus: An <I>Ab initio</I> Study of the Reaction of Hydrogen Atom and Methyl Radical With Phosphine and Methylphosphine
JF  - Australian Journal of Chemistry
JO  - Aust. J. Chem.
Y1  - 1995
VL  - 48
IS  - 2
SP  - 175
EP  - 184
KW  - 
UR  - https://doi.org/10.1071/CH9950175 
N2  - Homolytic substitution reactions of hydrogen atom and methyl radical at the phosphorus atom in phosphine and methylphosphine have been examined by high-level ab initio molecular orbital theory. MP4SDTQ/6-31G**//MP2(FC)/6-31G** calculations predict that free-radical attack at the phosphorus atom in phosphines is facile, with energy barriers of 14-33 kJ mol-1 and likely to involve hypervalent phosphoranyl radical intermediates. These intermediates, in turn, are found to have dissociative energy barriers of 10-31 kJ mol-1, depending on leaving group, and are unlikely to undergo pseudorotation prior to dissociation. MP5/6-31G**//MP2/6-31G** calculations indicate that permutational isomerism of phosphoranyl radical is likely to involve barriers of 145 and 127 kJ mol-1 for mechanisms involving transition states of D4h and C4v symmetry respectively. 
ER  -

