Addition of monosubstituted diazoalkanes, N 2CHR (R = Ph, p-Tolyl, tBu, Cy), to the bis(imino) pyridine iron dinitrogen complex, ( iPrPDI)Fe(N 2)2, at 23 °C in benzene-d 6 resulted in rapid cleavage of the N-N bond to yield the iron nitrile and imine complexes, ( iPrPDI)FeNCR and ( iPrPDI) FeHNCHR, respectively. Aryl azines were also cleaved with ( iPrPDI) Fe(N 2) 2 and yielded the same products. Mechanistic studies support a pathway involving initial formation of an iron alkylidene followed by rapid [4π + 2π] cycloaddition with another equivalent of diazoalkane. Subsequent rate-determining 1,3-hydrogen migration followed by retrocycloaddition yields the observed products.
All Science Journal Classification (ASJC) codes
- Colloid and Surface Chemistry