Bis(cyclopentadienyldicarbonyliron) ([CpFe(CO)(2)](2)) serves as a carbon monoxide source in carbonylative coupling reactions. Treatment of aryl iodides with primary amines in the presence of DBU and [CpFe(CO)(2)](2) under palladium catalysis provides the corresponding benzamides in good yields. Similar reactions with phenols and thiols provide the corresponding benzoate esters and thioesters, respectively. A catalytic amount of DMAP as an additive promoted the carbonylative coupling reactions with primary alcohol and secondary amine.