CARBON-FLUORINE BOND ACTIVATION BY IRON .1. C-F BOND-CLEAVAGE INDUCEDBY ADDITION OF PHOSPHINES OR THIOLS TO A PERFLUOROVINYLDIIRON COMPLEX

Citation
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
Citations number
39
Categorie Soggetti
Chemistry Inorganic & Nuclear","Chemistry Inorganic & Nuclear
ISSN journal
0022328X
Volume
533
Issue
1-2
Year of publication
1997
Pages
177 - 185
Database
ISI
SICI code
0022-328X(1997)533:1-2<177:CBABI.>2.0.ZU;2-7
Abstract
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.