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Published April 16, 2003 | public
Journal Article

Gas-Phase Synthesis of Charged Copper and Silver Fischer Carbenes from Diazomalonates: Mechanistic and Conformational Considerations in Metal-Mediated Wolff Rearrangements

Abstract

Copper(I) and silver(I) Fischer carbenes are synthesized in the gas phase. Various diazomalonate-based compounds with an attached metal ion are introduced into the gas phase by electrospray ionization and subjected to collisional activation. Loss of N2 generates a metastable Fischer carbene, which subsequently undergoes Wolff rearrangement and loss of CO. Further excitation leads to the loss of another CO molecule and the generation of a stable Fischer carbene. Isotopically labeled compounds are utilized to confirm the assignment of the products resulting from this process. DFT calculations are used to evaluate various mechanistic possibilities and to quantitatively assess the energetics of reactants and products. Silver(I) is shown to be more effective in facilitating Wolff rearrangement than copper(I), although both are more effective when compared to spectator charges such as sodium or a fixed quaternary nitrogen. Carbenes are not produced when copper(II), nickel(II), or a proton is used to form a quasi-molecular ion from the diazomalonate carbene precursor. Finally, trapping of the Fischer carbene by various functional groups attached through the open coordination site of the metal is investigated.

Additional Information

© 2003 American Chemical Society. Received 29 August 2002. Published online 19 March 2003. Published in print 1 April 2003. The authors gratefully acknowledge funding provided by NSF (Grant CHE-9727566), the Beckman Institute Foundation, the California Institute of Technology, the Camille and Henry Dreyfus Foundation (New Faculty Award to B.M.S.), and Abbott Labs (graduate fellowship to J.A.M.).

Additional details

Created:
August 19, 2023
Modified:
October 24, 2023