Manganese carbonyl derivatives based on Keggin- or Dawson-type polyoxoanions

The reactions of [Mn(CO)5]Br with saturated Keggin- or Dawson-type polyoxometalate precursors in the CH3CN/H2O mixed solvent have led to the formation of a series of compounds based on polyoxoanions and manganese carbonyl groups [Mn(CO)3(CH3CN)3]n[α-XM12O40] [n = 3, X = PV, M = MoVI (1), WVI (2)], [Mn(CO)3(CH3CN)3]n[α-XM12O40]·1.5H2O [n = 4, X = SiIV, M = MoVI, (3)], [Mn(CO)3(CH3CN)3]nH[α-XM12O40] [n = 3, X = GeIV, M = MoVI (4)] and [Mn(CO)3(CH3CN)3]6[α-X2M18O62]·H2O [X = PV, M = MoVI (5), WVI (6); X = AsV, M = MoVI (7), WVI (8)], which have been characterized by elemental analyses, IR spectra, X-ray photoelectron spectroscopy (XPS), thermogravimatric (TG) analyses and single-crystal X-ray diffraction. 1, 2 and 4 are isomorphous and crystallize in the trigonal space group P-3. While 5–8 are also isostructural and belong to the monoclinic space group P2(1)/c, but 3 crystallizes in the triclinic space group P-1. Single-crystal X-ray diffraction analyses indicate that 1–8 commonly consist of [Mn(CO)3(CH3CN)3]+ cations and polyoxoanions, which are combined by electrostatic interaction.

► Eight manganese carbonyl derivatives based on Keggin or Dawson POMs were obtained.
► All reactions were induced in acetonitrile–water (1:2 vol) mixed solvent.
► These compounds have been characterized by IR spectra, XPS, TG analyses.
► All compounds consist of [Mn(CO)3(CH3CN)3]+ cations and polyoxoanions.
► POA packing arrangements of 5–8 form cylindrical channels along the a axis.