"Heavy fluorous" cyclopentadienes and cyclopentadienyl complexes with three to five ponytails: facile syntheses from polybromocyclopentadienyl complexes, phase properties, and electronic effects.
The reactions between [(eta5-C5H(5-x)Br(x))M(CO)3] (M = Re, Mn; x = 1, 3, 4, 5) and [IZn[(CH2)(n)R(f8)]] (n = 2, 3; R(f8) = (CF2)7CF3) in the presence of [Cl2PdL2] catalysts give the title complexes [[eta5-C5H(5-x)[(CH2)(n)R(f8)]x]M(CO)3]. In the case of x = 5, the major product is actually [[eta5-C5H[(CH2)(n)R(f8)]4]M(CO)3], in which one of the bromides has been substituted by hydride. Minor amounts of multiple hydride substitution products are formed, all of them readily separable on fluorous silica gel. Irradiation of the manganese complexes in CF3C6H5/MeOH/ether gives uncoordinated cyclopentadienes, which can be deprotonated and reattached to other metals. Partition coefficients have been measured (CF3C6F11/toluene): complexes with three or more ponytails are highly fluorophilic, with values of > 99.8: < 0.2. The IR [symbol: see text]CO bands have been used to probe the inductive effects of the ponytails at the metal centers.
Dinh
Long V
LV
Institut für Organische Chemie, Friedrich-Alexander-Universität Erlangen-Nürnberg, Henkestrasse 42, 91054 Erlangen, Germany.
Gladysz
John A
JA