The synthesis, characterization and reactivity of low-coordinate, low-valent transition metal complexes featuring m-terphenyl isocyanides are discussed. For several years, encumbering m-terphenyl isocyanide ligands have been utilized as isolobal surrogates to carbon monoxide for the explicit purpose of generating stable and/or isolable complexes that embody the spirit of the binary unsaturated metal carbonyls. In several cases, m-terphenyl isocyanides of common substitution patterns (i.e. 2,6-(2,4,6-Me3C6H2)C6H3 and 2,6-(2,6-(i-Pr)2C6H3)C6H3) allow for the generation of unsaturated metal isocyanides that mimic their binary carbonyl analogues. However, in certain cases, this simple isocyanide for CO substitution fails with respect to the isolobal electronic structure analogy at the metal center. The factors governing this failure for middle and late transition metals are discussed and next generation m-terphenyl isocyanide ligands are presented that show promise in overcoming this apparent electronic structure breakdown.

Subtleties of the isocyanide for carbonyl isolobal substitution for middle and late transition metals

247th National Meeting (2014)

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