Exposure of the manganese pentacarbonyl halides [Mn(CO)5X] (X = CI, Br or I), to 6oCo y-rays a t 77 K givas an S = centre having a g ca. 2 and a large hyperfine coupling to 65Mn and the halogen nuclei. The results are interpreted in terms of electron addition into a cs* orbital involving mainly the metal d, a 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 = g.
Diphenyland diethyl-silane react with an excess of octacarbonyldicobalt to give compounds of the formula R,SiCo,(CO),, ( R = Et, Ph). High resolution i.r. and mass spectra strongly suggest that these derivatives contain nonacarbonyltricobaltmethoxy-and tetracarbonylcobalt-groups directly bonded to silicon. The corresponding hydridotetracarbonylcobaltand heptacarbonyldicobalt-silicon compounds appear to be intermediates in the reactions.
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