Challenges in cyclometalation: steric effects leading to competing pathways and η1,η2-cyclometalated iridium(iii) complexes?

Dalton Transactions Pub Date: 2018-08-15 DOI: 10.1039/C8DT02639D

Abstract

The iridation of (R)-N,N-dimethyl-1-(1-naphthyl)ethylamine in the presence of a base afforded an assortment of products ranging from organic molecules to coordinated systems and cyclometalated complexes. The transformation affirmed the postulation where steric effects within the coordination sphere favor a β-hydride elimination-like decomposition pathway, competing alongside ortho-metalation, thus leading to iminium intermediates. The same procedure also generated an unprecedented carbocyclic η12-cycloiridated species that could not be attained from the direct cyclometalation of its organic ligand.

Graphical abstract: Challenges in cyclometalation: steric effects leading to competing pathways and η1,η2-cyclometalated iridium(iii) complexes
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