TY - JOUR
T1 - Solution structure and dynamic behaviour of two isomers of [Fe3(CO)9{P(OR3)}3] (R = Me, Et, or Ph) derivatives
AU - Aime, Silvio
AU - Botta, Mauro
AU - Gambino, Olimpia
AU - Gobetto, Roberto
AU - Osella, Domenico
PY - 1989
Y1 - 1989
N2 - The reaction between [Fe3(CO)12] and P(OR)3 (R = Me, Et, or Ph) in the presence of the bimetallic catalyst [{Fe(CO)2(PPh3)(SEt)}2] affords two 1,2,3-trisubstituted isomers which rapidly interconvert at room temperature on the n.m.r. time-scale. The solution structures and dynamics have been elucidated for both isomers by means of variable-temperature 31P and 13C n.m.r. studies. In polar solvents the major isomer shows a [Fe3(CO)12]-like structure whereas the minor one contains only terminally bonded CO groups. The observation of three equally intense carbonyl resonances in the low-temperature-limiting spectra (R = Me or Et) supports a D3 structure for this isomer. The equilibration of axial CO ligands occurs readily as the temperature is increased; this rearrangement may be ascribed to the motion of the Fe3 triangle inside the polyhedral cloud of ligands or alternatively to an interconversion between a left-hand screw with a right-hand screw.
AB - The reaction between [Fe3(CO)12] and P(OR)3 (R = Me, Et, or Ph) in the presence of the bimetallic catalyst [{Fe(CO)2(PPh3)(SEt)}2] affords two 1,2,3-trisubstituted isomers which rapidly interconvert at room temperature on the n.m.r. time-scale. The solution structures and dynamics have been elucidated for both isomers by means of variable-temperature 31P and 13C n.m.r. studies. In polar solvents the major isomer shows a [Fe3(CO)12]-like structure whereas the minor one contains only terminally bonded CO groups. The observation of three equally intense carbonyl resonances in the low-temperature-limiting spectra (R = Me or Et) supports a D3 structure for this isomer. The equilibration of axial CO ligands occurs readily as the temperature is increased; this rearrangement may be ascribed to the motion of the Fe3 triangle inside the polyhedral cloud of ligands or alternatively to an interconversion between a left-hand screw with a right-hand screw.
UR - http://www.scopus.com/inward/record.url?scp=37049084083&partnerID=8YFLogxK
U2 - 10.1039/DT9890001277
DO - 10.1039/DT9890001277
M3 - Article
SN - 1472-7773
SP - 1277
EP - 1281
JO - Journal of the Chemical Society. Dalton Transactions
JF - Journal of the Chemical Society. Dalton Transactions
IS - 7
ER -