77307-41-6Relevant academic research and scientific papers
Radical pathways in substitutions of (η5-C5H5)Fe(CO)2(η 1-C5H5) and related reactions
Fabian, Benedict D.,Labinger, Jay A.
, p. 659 - 664 (2008/10/08)
The η1-cyclopentadienyl complex (η-C5H5)Fe(CO)2(η1-C 5H5) (1) undergoes unexpectedly facile CO substitution by phosphorus ligands. Evidence is presented that this involves a radical chain mechanism, wherein (η-C5H5)Fe(CO)2 is generated and undergoes rapid substitution, followed by transfer of C5H5 from 1 to (η-C5H5)Fe(CO)L. The resulting (η-C5H5)Fe(CO)L(η1-C5H 5) was isolated only for L = P(OPh)3 or P(O-i-Pr)3. For L = P(OR)3 (R = Me or Et) an Arbuzov-like rearrangement leads to (η-C5H5)Fe(CO)(P-(OR)3)(PO(OR) 2), while for L = PR3 a redox reaction with chlorinated solvent gives [(η-C5H5)Fe(CO)(PR3)2] + Cl-. With L = PMe3, [(η-C5H5)Fe(CO)(PMe3)2] +(C5H5)- was obtained. The η1-allyl analogue undergoes the same rapid radical-chain substitution mechanism but none of the subsequent reactions found for 1.
