CO-induced ring-slippage reactions of molybdenocene and tungstenocene carbonyl complexes. Electrochemical and elevated-pressure infrared evidence for an electron-transfer catalysis

Abstract

Infrared studies at a CO pressure of 120 bar show (1]s-C s H 5 hW(CO) to be completely resistant to an excess of CO in the absence of oxidants, but cyclovoltammetric measurements with this complex and with (1]3-C s H s)(1]5-C s H s) W (CO) 2 in THF solution at 0 0 C indicate that the ring-slipped dicarbonyl complex is catalytically generated by a one-electron oxidation of the tungstenocene monocarbonyl under CO at ambient pressure. Similar results are found for the reaction of (1]s-CsHshMo(CO) with CO.