Abstract
Cobalt-mediated decarboxylative Glaser-like C–C bond coupling of carboxylates has been studied in the gas phase using collision-induced dissociation (CID) multistage mass spectrometry (MSn) experiments. Both the identity of the carboxylate RCO2– (R = Me, HC≡C, MeC≡C, and PhC≡C) and the nuclearity of the complex ([CoCl(O2CR)2]– versus [Co2Cl3(O2CR)2]–) play a role in the types of reactions observed and their relative activation energies. In the first stage of CID, the mononuclear complex [CoCl(O2CMe)2]– undergoes decarboxylation, while the dinuclear [Co2Cl3(O2CMe)2]– undergoes cluster fission to yield [CoCl3]–; all acetylenic carboxylate complexes [CoCl(O2CR)2]– and [Co2Cl3(O2CR)2]– undergo decarboxylation. Isolation of the decarboxylated products followed by a second stage of CID results in a second decarboxylation event for all systems except for [CoCl(Me)(O2CMe)]–, which undergoes bond homolysis. In the final stage of CID, all acetylenic complexes undergo Glaser coupling, forming reduced Co anions. Overall dinuclear cobalt clusters are superior to mononuclear complexes at promoting decarboxylation and reductive coupling. The order of reactivity among the acetylide ligands is PhC≡C > MeC≡C > HC≡C.
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