Abstract
Abstract The addition of the anionic alkynyl complex [(OC)5W-CC-CMe3]−NEt4+ to unsaturated hydrocarbons of cationic complexes gives the thermolabile vinylidene bridged compounds (OC)5W=C=C(CMe3)(μ-hc)MLn [(μ-hc)MLn = (η1-C2H4)Re(CO)5 (1a), (η2-C3H5)Mo(η5-C5H5)(CO)(NO) (2), (η4-C6H4R)Fe(CO)3 (3a,b), (η4-C7H9)Fe(CO)3 (4a), (η5-C6H6)Mn(CO)3 (5a), (η6-C7H7)M(CO)3 M = Cr (6), W (7)]. At higher temperatures compounds 1a and 5a undergo elimination of the W(CO)5 fragment and 1,2 shift of the vinylidene group from the middle to the terminal C atom of the CC-tBu group. The 1,4-cycloheptadienyl complex 4a isomerizes at temperatures above −30°C to give the 1,3-cycloheptadienyl derivative 4b which was characterized by X-ray diffraction.
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