Due to the ability of serving as 1,1-synthons, isonitriles lend themselves to a variety of annulations where they serve as a one-carbon component in assembly of carbo- or heterocycles (e.g., [4+1] annulations pioneered by Curran) or, with a change of reactant topology, as two-atom components in the assembly of heterocycles.Our hypothesis was this behavior should be associated wtih additional state-crossings that corresponds to intramolecular charge and spin-transfer between nitrogen and carbon. Understanding of such dynamic state interconversion may unlock new electronic effects, not available to alkynes. From the practical perspective, such conceptual understanding can lead to the design of more efficient radical cascades.
Calculations were carried with the Gaussian 09 software package, using the (U)M06-2X DFT functional (with an ultrafine integration grid of 99,590 points) with the 6-311++G(d,p) basis set for all atoms except of Sn and Ge, for which we have used the Def2-QZVPP basis set. Grimme’s D3 version (zero damping)for empirical dispersion was also included. Frequency calculations were conducted for all structures to confirm them as either a minimum or a Transition State (TS). Intrinsic Reaction Coordinates (IRC) were determined for the TS of interest. Barriers were evaluated from isolated species due to formation of complexes for some systems, but not all of them. We performed Natural Bond Orbital (NBO) analysis on key intermediates and transition states. NBO deletions were performed at the UHF/6-311G(d) level of theory unless otherwise noted. Spin density was evaluated from the NBO analysis data. The Gibbs Free energy values are reported at 298 K, unless noted otherwise. We have used GoodVibes by Funes-Ardoiz and Paton to obtain the temperature-corrected Gibbs Free energies for calculating the temperature effects on selectivity in multifunctional substrates.