The bis(hexacarbonyldicobalt) complexes of cyclic diynes with sila‐, thia‐ and selena‐substituted acetylene units have been isolated. The structural features of these complexes have been elucidated by means of X‐ray diffraction analyses on single crystals. In three cases ( 24′ , 25′ and 29′ ) the X‐ray investigations show bis(pentacarbonyldicobalt) complexes instead of bis(hexacarbonyldicobalt) ones. Their empty coordination sites are each occupied by divalent chalcogen moieties from the opposite side of the molecule affording distorted C 2 Co 2 cores. These results corroborate the possibility of intramolecular activation in Pauson−Khand reactions of chalcogen‐containing substrates. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004)
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Werz et al. (2004) studied this question.
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