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Updated: Aug 31, 2025

Accessing Valuable Ligand Supports for Transition Metals: A Modified, Intermediate Scale Preparation of 1,2,3,4,5-Pentamethylcyclopentadiene
Published on: March 20, 2017
Introducing the Perfluorinated Cp* Ligand into Coordination Chemistry
Robin Sievers1, Malte Sellin1,2, Susanne M Rupf1
1Freie Universität Berlin, Institut für Chemie und Biochemie, Anorganische Chemie, Fabeckstraße 34-36, 14195, Berlin, Germany.
Abstract:
The reaction of AgBF4 and [Rh(COD)Cl]2 (COD=1,5-cyclooctadiene) in presence of [NEt4 ][C5 (CF3 )5 ] afforded the fluorocarbon soluble complex [Rh(COD)(C5 (CF3 )5 )] by salt metathesis. This complex represents the first example for a successful coordination of the weakly basic [C5 (CF3 )5 ]- ligand, since its first synthesis in 1980. In addition to [Rh(COD)(C5 (CF3 )5 )] also the byproduct [Rh(COD)(C5 (CF3 )4 H)] was isolated and fully characterized. Accompanying DFT studies showed that the interaction energy of the [C5 (CF3 )5 ]- ligand towards the 12-electron fragment [Rh(COD)]+ is ≈70 kcal mol-1 lower in comparison to [C5 (CH3 )5 ]- due to reduced electrostatic interactions and weaker π-donor properties of the ligand. The quantitative but reversible substitution of the [C5 (CF3 )5 ]- ligand by toluene, converting it into a weakly coordinating anion, experimentally proved the extraordinary weak bonding interaction.
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