Syntheses and reactions of bromotetrafluorophenyl(cyclopentadienyl)dicarbonyliron derivatives

The Reaction of the [CpFe(CO)2]− Anion with Pentafluorochlorobenzene: Nucleophilic Aromatic Substitution by Halogen-Metal Exchange

“…[3d, 5,11,12] In contrast, the yield of the nucleophilic substitution product, C 6 F 5 Fp, in the reaction of FpK with C 6 F 5 Cl is higher at room temperature (50 ± 60 %) than at À 50 8C (13 ± 20 %), when the dimer Fp 2 and other products of the redox process [b] are primarily formed (entries 1 ± 3 Table 1). These include chloroperfluoropolyphenyls C 6 F 5 H and FpCl, though only traces of the latter were observed.…”

“…recently in nucleophilic vinylic substitution reaction between Fp À and chlorodifluorostyrene. [17] Also worth mentioning is one more work reporting that the use of FpLi in ether/hexane solution in the reaction with C 6 F 4 Hal 2 (all isomers, Hal Cl, Br) furnishes the monosubstitution products FpC 6 F 4 Hal in moderate yield, [11] yet nothing is known about the course of the same reactions in THF. This data is hardly compatible with our current results, and does not help us in answering the question why ether and large cations caused similar effects.…”

Amine-catalyzed substitution in CpFe(CO)2I by phosphine and bisphosphine ligands

“…46 IR spectra were recorded in KBr on an FT-IR spectrometer (NEXUS, Thermo Nicolet). 1 H, 13 C, and 31 P{H} NMR spectra were recorded on an NMR spectrometer (Avance III, Bruker; 600 MHz for 1 H, 151 MHz for 13 C, and 243 MHz for 31 P) in DMSO-d 6 , CD 3 OD, or CDCl 3 solution. The chemical shifts are expressed in parts per million.…”

“…1 H NMR (CDCl 3 ) δ 7.61 (dd, J = 6.0, 2.8 Hz, 9H, CH ar ), 7.40 (ddd, J = 12.1, 6.8, 3.1 Hz, 6H, CH ar ), 5.49 (d, J = 1.3 Hz, 5H, Cp). 13 Synthesis of compound 4. DIPA (46 µl, 0.329 mmol) was added to a mixture of CpFe(CO) 2 I (0.1 g, 0.329 mmol) and dppe (0.131 g, 0.329 mmol) in freshly distilled, degassed toluene (3 mL) under an argon atmosphere.…”

“…Substitution of the halide and/or CO ligands in half-sandwich complexes CpFe(CO) 2 X (Cp = η 5 -C 5 H 5 ; X = halogen) is a useful route to a variety of organoiron compounds. [1][2][3][4][5][6][7][8][9][10][11][12][13] However, such reactions often require harsh conditions and have poor selectivity. For example, the reaction of CpFe(CO) 2 I (1) with triphenylphosphine requires long refluxing in benzene and leads to a mixture of the products of iodide and CO substitution (2 and 3, respectively, Scheme 1).…”