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Structural Properties of Bis(hexacarbonyldicobalt) Complexes with Heteroatoms Next to the Former Triple Bonds − A Contribution to the Mechanism of the Pauson−Khand Reaction
Author(s) -
Werz Daniel B.,
Schulte J. Hilko,
Rausch Bernhard J.,
Gleiter Rolf,
Rominger Frank
Publication year - 2004
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/ejic.200300862
Subject(s) - chemistry , chalcogen , intramolecular force , heteroatom , molecule , pauson–khand reaction , triple bond , divalent , acetylene , stereochemistry , coordination complex , crystallography , metal , polymer chemistry , organic chemistry , ring (chemistry) , double bond
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)