Tetramethyl(perfluoroalkyl)cyclopentadienyl rhodium(I) complexes with ethylene or diene ligands. Crystal structure of [(η5-C5Me4C6F13)Rh(CO)2]

Synthesis and Coordination Chemistry of Fluorinated Cyclopentadienyl Ligands

“…However, by using four methyl substituents on the other positions, the electronic effects can be balanced which allowed the successful preparation and structural characterization of rhodium complexes. 63 64 65 In rare cases, incorporation of fluoroalkyl groups is also possible via reaction of perfluoroalkyl iodides with metal cyclopentadienyl complexes. 66,67…”

“…However, by using four methyl substituents on the other positions, the electronic effects can be balanced which allowed the successful preparation and structural characterization of rhodium complexes. [63][64][65] In rare cases, incorporation of fluoroalkyl groups is also possible via reaction of perfluoroalkyl iodides with metal cyclopentadienyl complexes. 66,67 Instead of completely perfluorinated alkyl substituents the use of ethylene spacers (-CH 2 -CH 2 -) has been a viable strategy in order to maintain the solubility in perfluorinated solvents, without decreasing the bonding interactions between the cyclopentadienyl ligand and the metal center significantly.…”

Fluorous Organometallic Chemistry

“…As expected, although these light fluorous complexes are soluble in perfluorinated solvents, they are not preferentially soluble in the fluorous phase of a fluorous-organic biphasic system. Later, Horváth [86,87]. Cleavage of the chloride-bridged dimer with PMe 3 or a series of pyridines generated rhodium(III) piano-stool monomers with single C 6 F 13 ponytails [88].…”

“…Cleavage of the chloride-bridged dimer with PMe 3 or a series of pyridines generated rhodium(III) piano-stool monomers with single C 6 F 13 ponytails [88]. Reduction in the presence of ethylene or various dienes, on the other hand, affords rhodium(I) bisalkene complexes (6b-e) [87].…”

Dehydration of (Perfluoroalkyl)tetramethylcyclopentenols

“…These include cyclopentadienes with one [9], two [10,11,12] or more [13,14] (perfluoroalkyl)ethyl chains, cyclopentadienes with silicon atoms directly bonded to the ring to separate electronic effects of the fluorous ponytail [15,16,17,18] and cyclopentadienes monosubstituted with perfluoroalkyl chains [9], which are difficult to handle or use for metal complexation. The last of the so far known types of fluorous cyclopentadienes is represented by the (perfluoroalkyl)tetramethylcyclopentadienes prepared in our group [16,19,20,21]. In the latter compounds the electrondonating effect of four methyl groups compensates for the opposite effect of the perfluoroalkyl chain bonded directly to the ring, providing stable precursors to ligands with electronic properties close to the unsubstituted cyclopentadienyl but steric properties comparable to pentamethylcyclopentadienyl.…”