Challenges in cyclometalation: steric effects leading to competing pathways and η1, η2-cyclometalated iridium(iii) complexes. Issue 37 (29th August 2018)

• Record Type: Journal Article
• Authors: Chen, Houguang Jeremy; Teo, Ronald Hong Xiang; Wong, Jonathan; Li, Yongxin; Pullarkat, Sumod A.; Leung, Pak-Hing
• Is Part Of: Dalton transactions. Volume 47:Issue 37(2018)
• Page Start: 13046
• Page End: 13051
• Publication Date: 2018-08-29
• Subjects: Chemistry, Inorganic -- Periodicals; Chemistry, Physical and theoretical -- Periodicals; Chemistry, Inorganic -- Periodicals; 546.05
• DOI: 10.1039/c8dt02639d
• Languages: English
• ISSNs: 1477-9226

Abstract

Abstract : The iridation of a known cyclometalating ligand led to several products, one of which is an olefin-directed carbocyclic iridacycle. The mechanistic pathways to the formation of these compounds were investigated. 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 η 1, η 2 -cycloiridated species that could not be attained from the direct cyclometalation of its organic ligand.