Phosphorus-carbon bond forming reactions of iron tetracarbonyl-coordinated phosphenium ions

Abstraction of chloride from [Fe(CO)4(PPh2Cl)] (1) in the presence of PPh3 leads to [Fe(CO)4(PPh2(PPh3))][AlCl4] (2), an iron complex of a phosphine-coordinated phosphenium ion. The PPh3 is readily displaced by ferrocene, leading to an electrophilic aromatic substitution reaction, and formation of [Fe(CO)4{PPh2Fc}] (3) (Fc = ferrocenyl). Alternately, chloride abstraction from 1 in the presence of ferrocene leads directly to 3, via a transient phosphenium ion complex. The transient phosphenium ion complex also reacts with N,N-diethylaniline, indole, and pyrrole to form the respective p-anilinyl, 3-indolyl, and 2-pyrryl phosphine complexes via electrophilic aromatic substitution. Chloride abstraction from [Fe(CO)4(PPhCl2)] in the presence of ferrocene leads to a double substitution reaction, forming [Fe(CO)4{PPhFc2}] (13).