•Group VIB metal carbonyl complexes contain a heteroacene ligand.•UV–vis spectra of the complexes are red-shift compared to that of the ligand.•X-ray crystal structures of all the carbonyl complexes were obtained.Group VIB metal carbonyl heteroacene complexes were synthesized and characterized. Single crystal X-ray diffraction confirms that all metal carbonyl complexes bond to the ligand through the phenanthroline unit. Their absorption spectra are red-shifted compared to that of the ligand and their cyclic voltammetry revealed that their reduction occurred at less reducing potentials than the corresponding reduction in ligand.This article describes the synthesis and characterization of group VIB metal carbonyl heteroacene complexes. Metal carbonyl complexes bond to the ligand through the phenanthroline unit and their structures are confirmed by single-crystal X-ray diffraction analysis.

•We investigated the reaction of a bimetallic iron–tin cluster Fe4(CO)16(μ4-Sn) with group V donors.•Fe4(CO)16(μ4-Sn) reacts with PPh3 to afford the phosphine derivative Fe4(CO)15(PPh3) (μ4-Sn).•Fe4(CO)16(μ4-Sn) reacts with SbPh3 to afford the trimetallic Fe4(CO)15(SbPh3) (μ4-Sn).•The structures of the new complexes were characterized by single-crystal X-ray diffraction analysis.The reaction of di-iron nonacarbonyl with triphenyl stannane yielded the bow-tie structured Fe4(CO)16(μ4-Sn), 1. 1 reacted with LPh3 to afford the corresponding derivatives Fe4(CO)15(LPh3)(μ4-Sn), (L = P, 2, L = Sb, 3) by CO substitution on Fe. 2 and 3 were characterized crystallographically by single-crystal X-ray diffraction techniques.We have investigated the reaction of a bimetallic iron–tin cluster Fe4(CO)16(μ4-Sn) with group V donors. Fe4(CO)16(μ4-Sn) reacts with LPh3 to afford the phosphine derivative Fe4(CO)15(PPh3) (μ4-Sn), L = LPh3, or reacts with SbPh3 to afford the trimetallic Fe4(CO)15(SbPh3) (μ4-Sn), L = SbPh3. The structures of the new complexes were characterized by single-crystal X-ray diffraction analysis.