R. Rumin et al., CARBON-FLUORINE BOND ACTIVATION BY IRON .1. C-F BOND-CLEAVAGE INDUCEDBY ADDITION OF PHOSPHINES OR THIOLS TO A PERFLUOROVINYLDIIRON COMPLEX, Journal of organometallic chemistry, 533(1-2), 1997, pp. 177-185
The reaction of phosphines PXYH (X=Y=P4 i-Pr; X=Ph, Y=H) or ethanethio
l with the perfluorovinyl compound [(Fe(CO)(3))(2)(mu-C(SMe)(CF3)CCF2)
] (l) proceeds with cleavage of one C-F bond and gives rise to unusual
ligand transformations. The multicenter processes involved lead to ne
w diiron complexes [(Fe(CO)(3)}(2)(mu-C(SMe)(CF3)C(PXY)CF)] (X = Y = P
h, 2a; X = Y-i-Pr, 2b; X = Ph, Y = H, 2c) and [(Fe(CO)(3))(2)(mu-C(SMe
)(CF3)C(SEt)CF)] (3). Mechanisms for these reactions are proposed. The
fluxional behavior of 2a and 3 has been investigated by variable-temp
erature C-13 NMR spectroscopy. The molecular structure of 2a has been
established by a single-crystal X-ray diffraction study. The Fe-2(CO)(
6) core contains an Fe-Fe bond of 2.633(1)Angstrom bridged by the six-
electron donor C(SMe)(CF3)C(PPh2)CF Ligand. 2a crystallizes in the tri
clinic space group P (1) over bar with a = 9.019(2), b = 9.550(2), c =
18.583(3)Angstrom, alpha = 101.06(2), beta = 92.53(2), gamma = 116.48
(2)degrees, R = 0.0419 for 3984 reflections.