(Cyclopentadienyl)dicarbonylmethyliron ((η⁵-C₅H₅)Fe(CO)₂CH₃, FpMe), a Seminal Transition-Metal Alkyl Complex: Mobility of the Methyl Group

Abstract

A review is presented of the chemistry of (η 5 -C 5 H 5 )Fe(CO) 2 CH 3 (1), with emphasis upon reactions in which the Fe-methyl bond is broken, e.g. insertions, eliminations, and migrations, including the capacity of 1 to be a useful catalyst.

Evidence for Iron‐Catalyzed α‐Phosphinidene Elimination with Phenylphosphine

“…Literature understanding of 1 and the observed reaction chemistry provide the basis for a working mechanistic hypothesis for this catalysis (Scheme ). Activation of 1 would arise from migratory insertion of the methyl ligand, rather than protonation, based on the relatively low acidity of these phosphine substrates and prior study of protonolysis and migratory insertion reactions at 1 . This proposal is buttressed by the persistence of 1 at the end of catalysis.…”

Iron distannanes (η5-C5H5)Fe(CO)2SntBu2SntBu2X, (X=Cl, OMe): Thermal and photochemical transformations to iron stannylstannylenes

“…Hence, the intramolecular CleSn and OeSn bond formation could be the driving force to facilitate the expulsion of the carbonyl ligand resulting in the observed complexes 3. This is reminiscent, but distinct from, the nucleophilic-assisted migration of the methyl group from Fe to a carbonyl group in FpCH 3 resulting in the formation of (h 5 -C 5 H 5 )Fe(CO)(COCH 3 )L [23]. More related to the current result is the thermal decomposition of related distannanes, BrR 2 SnSnR 2 Br, involving rupture of the SneSn bond facilitated by bromine migration to form R 2 SnBr 2 and R 2 Sn [24].…”

Synthesis and migration insertion polymerization (MIP) of CpFe(CO)2(CH2)6PPh2(FpC6P) for PFpC6P: macromolecule stability, degradability and redox activity

“…[40][41][42] When the complexes were incorporated into macromolecular chains via MIP, enhanced thermal stability was observed. [40][41][42] When the complexes were incorporated into macromolecular chains via MIP, enhanced thermal stability was observed.…”

“…28 We have recently developed a new polymerization technique, named migration insertion polymerization (MIP), using CpFe(CO) 2 (CH 2 ) 3 PPh 2 (FpC3P) as a monomer. 30 In solution, intramolecular cyclizations via Fe-P coordination are major reactions, especially at low FpC3P concentration. FpC3P can undergo a migration insertion reaction (MIR) at elevated temperature (>40°C).…”