A scorpionate-type ligand was produced via a Re(CO)3 mediated template reaction. The ligand is composed of two equivalents of diiminoisoindoline and an activated nitrile to form a metal-bound amidinate. This chemistry differs from previously observed templating reactions with diiminoisoindoline, where planar bidentate ligands are formed. The products of these template reactions are six-coordinate Re complexes, with a facial arrangement of carbonyls, a neutral tridentate activated nitrile chelate that tilts out of the plane of coordination similar to the recently synthesized semihemiporphyrazines, and a free halide counterion. Seven examples of chelates can be produced from these reactions, depending on the nitrile activated; structures including activated alkyl and aromatic nitriles resulting in a sp3 carbon on one of the two diiminoisoindoline units.

Re(CO)3-templated scorpionate synthesis through nitrile activation

254th National Meeting (2017)

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