TY - JOUR
T1 - Preparation and ESR of phosphorus spiro compounds : part III
AU - Rothuis, R.
AU - Font Freide, J.J.H.M.
AU - van Dijk, J.M.F.
AU - Buck, H.M.
PY - 1974
Y1 - 1974
N2 - The synthesis of 2,2'-biphenylenediphenylphosphonium, 2,2'-biphenylenephenylbenzylphosphonium and 2,2'-biphenylenephenyl(p-nitrophenyl)phosphonium salts is described. The related phosphoranyl radicals I, IV and V, generated by electrochemical reduction, are measured by ESR spectroscopy. A similar procedure is followed for the radicals II and III; related phosphonium compounds are described in the literature. The small values of the phosphorus doublet splitting constants are an indication for a tetrahedron (T) like configuration of the phosphorus. The odd electron is delocalized in the aromatic ligands and the five 3-d orbitals of the phosphorus. It is shown that the spin- and odd electron density distribution depends on the electron affinity of the aryl ligands. This is confirmed by quantum chemical calculations.
AB - The synthesis of 2,2'-biphenylenediphenylphosphonium, 2,2'-biphenylenephenylbenzylphosphonium and 2,2'-biphenylenephenyl(p-nitrophenyl)phosphonium salts is described. The related phosphoranyl radicals I, IV and V, generated by electrochemical reduction, are measured by ESR spectroscopy. A similar procedure is followed for the radicals II and III; related phosphonium compounds are described in the literature. The small values of the phosphorus doublet splitting constants are an indication for a tetrahedron (T) like configuration of the phosphorus. The odd electron is delocalized in the aromatic ligands and the five 3-d orbitals of the phosphorus. It is shown that the spin- and odd electron density distribution depends on the electron affinity of the aryl ligands. This is confirmed by quantum chemical calculations.
U2 - 10.1002/recl.19740930503
DO - 10.1002/recl.19740930503
M3 - Article
SN - 0165-0513
VL - 93
SP - 128
EP - 129
JO - Recueil des Travaux Chimiques des Pays-Bas
JF - Recueil des Travaux Chimiques des Pays-Bas
IS - 5
ER -