Relying on the isoloble relationship between isocyanides (CNR) and CO, our group has used the m-terphenyl isocyanide CNArMes2 (Mes = C6H3-2,4,6-Me3) to isolate a mononuclear [Co(CNArMes2)4]+ species analogous to [Co(CO)4]+. Characterization of this diamagnetic compound shows a square planar geometry about the Co center, disagreeing with previous work pertaining to the cobalt carbonyl cationic species. In order to more fully understand the nature of our complex compound with respect to the carbonyl species a thorough computational analysis has been conducted. The current work shows that the calculated ground state geometries of both the cobalt carbonyl and model cobalt isocyanide (CNCH3, CNC6H3-2,6-Me2) cations are dependent on the functional chosen. The commonly used B3LYP functional calculates the C2v triplet state to be the ground state for all three species. However, when other functionals (BLYP, O3LYP, OLYP and G96LYP) are used, the D4h singlet ground state is more often found to be the ground state. The nature of the B3LYP functional has been explored by adjusting the amount of Hartree Fock exchange mixed into the functional to gauge the impact on the calculated stretching frequencies of the CO and CN fragments

Computational investigations of the isomeric preference of [Co(CO)4]<sup>+ </sup>and [Co(CNR)4]<sup>+</sup>

243rd National Meeting (2012)

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Computational investigations of the isomeric preference of [Co(CO)4]+ and [Co(CNR)4]+

Computational investigations of the isomeric preference of [Co(CO)4]⁺and [Co(CNR)4]⁺