Solventless migratory-insertion reactions of substituted cyclopentadienyl iron complexes induced by electron donor ligands

Abstract

Reaction between solid (C5H5)Fe(CO)2CH3 and a range of solid phosphine ligands, L (L = PPh3, P(m-CH3C6H4)3, P(p-CH3C6H4)3, P(p-FC6H4)3, P(p-ClC6H4)3, PCy3) occurred in the absence of solvent in the melt phase to give the migratory-insertion products, (C5H5)Fe(CO)(COCH3)(L). The reaction was more rapid with small electron withdrawing ligands. Insertion reaction between (RC5H4)Fe(CO)2R' (R = H, CH3; R' = CH3, CH2Ph) and gaseous ligands such as SO2 and CO were also studied. The insertion of SO2 occurred readily for all the substrates investigated, but CO insertion did not occur (< 1 %) using the solventless reaction condition.

Migration Insertion Polymerization (MIP) of Cyclopentadienyldicarbonyldiphenylphosphinopropyliron (FpP): A New Concept for Main Chain Metal-Containing Polymers (MCPs)

“…However, FpP undergoes intramolecular cyclic reactions in diluted organic solvents (see Supporting Information). 20 Since MIR can also occur in solid state, 18,21 bulk polymerization of FpP was performed at 70 °C to suppress intramolecular cyclic reactions. During the polymerization, the viscosity of the system gradually increased until glass-like solid material was produced with the stir bar frozen inside the product.…”

Advances in organometallic synthesis with mechanochemical methods

“…37,38 In this context, Coville and his collaborators must be recognized for their pioneering studies in solvent-free synthesis, [39][40][41] including migratory insertion and ligand substitution reactions induced by melting (e.g., the reaction depicted in eqn (1), which generates 90% of the insertion product after 4 h at 80 °C). 42 ð1Þ Many of these tranformations, however, including thermally induced ligand isomerizations and reactions at surfaces, do not involve the application of mechanical energy, and are not, strictly speaking, mechanochemical in nature. The range of organometallic complexes synthesized through truly mechanochemical methods is relatively small, but growing; some examples are provided in Fig.…”

Chemistry 2.0: Developing a New, Solvent-Free System of Chemical Synthesis Based on Mechanochemistry

“…That eutectic formation does not guarantee a chemical reaction was shown by Munyaneza et al in comparing solvent-free ligand exchange on ruthenium and iron cyclopentadienyl complexes. 104,105 While Fe(C 5 H 4 CH 3 )(CO) 2 I readily reacts with phosphines in the melt, ruthenium analogues reacted poorly, regardless of melting: Ru(C 5 H 4 CH 3 )(CO) 2 I and triphenylphosphine form a eutectic melting at 36 °C, but no reaction took place below 70 °C.…”