Synthesis of aminooxycarbene complexes of iron with N-alkyl, -allyl, and -carbamoyl groups

Abstract

The aminoozycarbene complex Cp(CO)/sub 2/Fe(double bond COCH/sub 2/CH/sub 2/NH)/sup +/ (I) is deprotonated by NaH to give Cp(CO)/sub 2/Fe(-COCH/sub 2/CH/sub 2/N)(II), whose nitrogen reacts with electrophiles. With Me/sub 3/O/sup +/, II yields the N-methyl carbene Cp(CO)/sub 2/Fe(double bond COCH/sub 2/CH/sub 2/NMe)/sup +/ (III). Reaction of II with allyl bromide yields the N-allyl carbene Cp(CO)/sub 7/Fe(double bond COCH/sub 2/CH/sub 2/NCH/sub 2/CH double bond CH/sub 2/)/sup +/ (IV), which under UV photolysis loses CO, allowing the allyl group to coordinate in Cp(CO)Fe(double bond COCH/sub 2/CH/sub 2/NCH/sub 2/CH double bond CH/sub 2/)/sup +/. The nitrogen of II adds to the carbon of methyl isocyanate; this is followed by isocyanate nitrogen attack on a coordinated CO ligand to give a carbamoyl-carbene complex, Cp(CO)Fe(double bond COCH/sub 2/CH/sub 2/NC(double bond O)N(Me)C double bond O (VI). Protonation of VI cleaves the carbamoyl ligand to give the N carbamoyl carbene Cp(CO)/sub 2/Fe(double bond COCH/sub 2/CH/sub 2/NC(double bond O)NHMe)/sup +/. These interesting new complexes are characterized by their /sup 1/H and /sup 13/C NMR and ir spectra. 20 references, 4 tables.