M. Buhl et al., X-ray structures and DFT calculations on rhodium-olefin complexes: Comments on the Rh-103 NMR shift-stability correlation, ORGANOMETAL, 19(26), 2000, pp. 5589-5596
The low-temperature X-ray structures of bis(eta (2)-ethene)(2,4-pentanedion
ato)rhodium(I) (1)- and bis(eta (2)-ethene)(1,1,1,5,5,5-hexafluoro-2,4-pent
anedionato)rhodium(I) (2) were determined. Very similar Rh-ethene coordinat
ion geometries are found in the solid state, i.e., 1, Rh-C = 2.127(5) Angst
rom, and 2, Rh-C = 2.121(3) Angstrom, in good accord with DFT calculations,
i.e., 1, RB-C = 2.132 Angstrom and 2, Rh-C = 2.136 Angstrom. The calculate
d Rh-103 NMR chemical shifts (GIAO-B3LYP/II level) for a range of bis(eta (
2)-alkene)(2,4-pentanedionato)rhodium(I) complexes also agree well with sol
ution NMR data. The empirical correlation between transition-metal shifts a
nd stability constants (Ohrstrom, L. Comm. Inorg. Chem. 1996, 18, 305) coul
d be confirmed for simple alkenes, since the computed relative Rh-alkene bi
nding energies were found to correlate with delta(Rh-103). I, contrast, che
lating or fluorinated alkenes showed large deviations from this correlation
. The steric and electronic effects on the Rh-alkene bond are discussed and
analyzed in terms of Bader's atoms-in-molecules theory, which revealed qua
litatively different binding modes of ethene and tetrafluoroethene to rhodi
um: ethene forms typical pi -complexes in the Dewar-Chatt-Duncanson model,
whereas tetrafluoroethene complexes are on the borderline to metallacyclopr
opanes.