Synthesis, structure and electrochemistry of ferrocenylethynylsilanes and their complexes with dicobalt octacarbonyl1

Add time:08/08/2019    Source:sciencedirect.com

Coupling of lithium ethynylferrocene to alkyl and aryl chlorosilanes and to silicon tetrachloride leads to the formation of a variety of ferrocenylethynylsilanes, [(η5-C5H5)Fe(η5-C5H4C2)]4−nSiRn (n=0–3, R=Me, Ph). An additional series of compounds [(η5-C5H5)Fe(η5-C5H4C2)]4−nSi(n-Bu)xRy (n=0–3, x+y=n, R=Me, Ph) result from competitive reactions of excess n-BuLi at the silicon centre. Dicobalt octacarbonyl reacts with the ferrocenylethynylsilanes to give dicobalt hexacarbonyl derivatives, but for the tris- and tetrakis-compounds coordination of Co2(CO)6 is limited to two of the alkyne units as a result of steric crowding around the silicon centre. The crystal and molecular structure of the complex [(η5-C5H5)Fe(η5-C5H4C–(Co2(CO)6)C]2Si[(CC-η5-C5H4)Fe(η5-C5H5)]2 has been determined from X-ray data. Electrochemical investigation of the ferrocenylethynylsilanes and their dicobalt complexes shows that the equivalent ferrocenyl redox centres in these molecules are non-interacting.

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