Studies of the interactions of the tungsten pentacarbonyl fluoride anion with carbon dioxide

Herein, it is shown that the CCDC reported structure of the piperdium salt of FCO5− is misidentified. Investigating of the reactions of CO2 and FW(CO)5− led to the isolation and structured characterization of the (HCO3)W(CO)5− anion. [Display omitted] The FW(CO)5− anion was synthesized by photolysis of W(CO)6 in tetrahydrofuran solution upon the addition of anhydrous PPNF or nBu4NF, and was characterized by infrared and 19F NMR spectroscopies. The complex was shown to be very unstable in solution in the absence of a CO atmosphere. Addition of CO2 to FW(CO)5− in THF provided no evidence of CO2 insertion into the W-F bond, instead affording a bicarbonate tungsten pentacarbonyl complex resulting from hydrolysis by adventitious moisture.