Synthesis, structural characterization and reactivity studies of a series of cobalt metalloanions, including a tetrakisisocyanide cobaltate supported by a novel m-terphenyl isocyanide ligand, CNArArF,(ArF = 3,5(CF3)2C6H3), are presented. Protonation of the metallate, Na[Co(CNArMes2)4] (Mes = 2,4,6-Me3C6H2-) affords HCo(CNArMes2)4, an isocyano analogue of HCo(CO)4. Like its carbonyl counterpart, HCo(CNArMes2)4 is shown to possess H+, H- and H-atom donor properties. Reactivity studies on HCo(CNArMes2)4 allow access to a variety of iminoacyls, allyls and carbenes that, in conjunction with kinetic studies, demonstrate the migratory aptitude of the hydride in this system. Ligand substitution reactions with HCo(CNArMes2)4 provide access to a variety of HCo(CNArMes2)3L species (L = XylylNC, t-BuNC, PMe3, PPh3, CO) that, upon deprotonation, afford the corresponding cobaltate anions. In studies that highlight m-terphenyl isocyanide ligation, a series of mixed carbonyl/isocyanide dicobalt dimers have also been prepared which serve as analogues to each isomer of Co2(CO)8, including the elusive D2d-symmetric isomer.

Isocyanide supported cobalt metallates, hydrides, and dimers

245th National Meeting (2013)

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