Abstract
Exposure of the manganese pentacarbonyl halides [Mn(CO)5X](X = Cl, Br or I), to 60Co γ-rays at 77 K gives an S=½ centre having a g ca. 2 and a large hyperfine coupling to 55Mn and the halogen nuclei. The results are interpreted in terms of electron addition into a σ* orbital involving mainly the metal dz2 and halide pz orbitals. A second centre having two apparent g values in the g= 6 region is also formed for all the three complexes. These again exhibit hyperfine coupling to 55M and to the halogen nuclei. Various structures are considered, and it is concluded that the most reasonable are cations formed by loss of an electron and one or more carbonyl groups with unpairing of the remaining electrons to give S=5//2.
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