Synthesis of fluorophenyl derivatives of iron, molybdenum and tungsten via B(C6F5)(3) and unusual carbon-fluorine bond reactions

The reaction between B(C6F5)(3) and [Fe(eta-C5H5)(CO)(2)Me] gave the unexpected product [Fe{C6F4C(O)Me-2}(eta-C5H5)(CO)] 1 which reacts with the donor molecules L = PMe3, PPh3 or (BuNC)-N-t giving [Fe{C6F4C(O)Me-2}(eta-C5H5)L].* Likewise [{Fe[C6F4C(O)Me-2](eta-C5H5)}(2)(mu-dppe)]* was formed from 1 and Ph2P(CH2)(2)PPh2 (dppe). The formation of the compound where L = PMe3 is shown to proceed via initial formation of [Fe{C6F4C(O)Me-2}(eta-C5H5)(CO)(PMe3)]* The reaction between B(C6F5)(3) and [M(eta-C5H5)(CO)(3)Me] (M = Mo or W) gave the compounds [M{C6F4C(O)Me-2}(eta-C5H5)(CO)(2)]. The compounds [M{C6F3X-5-C(O)Me-2}(eta-C5H5)(CO)(2)]* (M = Mo or W) where X = H were prepared from the compounds where X = F via unusual C-F bond-activation reactions. The compound [Fe{C6F3H-5-C(O)Me-2}(eta-C5H5)(PMe3)] was prepared by photolysis of a mixture of [Fe{C6F3H-5-C(O)Me-2}(eta-C5H5)(CO)] and PMe3. The asterisk indicates the crystal structure has been determined.