The integration of a mixed ligand environment involving an organometallic and Werner-type ligand along with the earth abundant cobalt metal in a high oxidation state has the potential for interesting reactivity. Complexes of the type [Co(CpR)(X-DAMP)(I)](I), where R = H for Cp; cyclopentadienyl or R = Me for Cp*; pentamethylcyclopentadienyl and X = R or S have been prepared by ligand substitution from [Co(Cp*)(I)2(CO)] with 1,2-(X)-diaminopropane (DAMP). The outer sphere iodide is readily exchanged with anions of various sizes such as BF4-, ClO4-, PF6-, and BArF (ArF = tetrakis[3,5-bis(trifluoromethyl)phenyl]) in order to aid in characterization. For example, we observe reversible CoIII/CoII reduction potentials of [(CpR)Co((X,X)-DPEN)(I)]BArF (DPEN = diphenylethylenediamine) at E°’ = -713 mV for Cp and E°’ = -932 mV for Cp* with respect to a Fc/Fc+ internal standard. This synthetic methodology was also applied in the attempted isolation of a de facto cyclometallated intermediate in cobalt catalyzed C-H activation of the same Co(III) species in the presence of monodentate electron rich phosphine or phosphite ligands. Preliminary findings suggest successful deprotonation of 2-phenylpyridine and subsequent coordination to Co(III). These findings, along with explorative chemistry for the synthesis of organometallic chiral amine-cobalt(III) complexes will be presented.

Ancillary ligand and outer-sphere anion exchange reactions involving {CpRCo(III)} for potential catalytic applications in inert bond activation

Macromolecular Chemistry: The Second Century

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ACS Spring 2020 National Meeting & Expo

The official archive and repository for all ACS Meetings & Expositions abstracts and select posters or presentations.