Competition between vinylidene rearrangement and 1, 2-insertion of carbon-disubstituted internal alkynes at a Cp*Ir(iii) complex. Issue 40 (2nd September 2015)

• Record Type: Journal Article
• Authors: Ikeda, Yousuke; Kodama, Shintaro; Tsuchida, Noriko; Ishii, Youichi
• Is Part Of: Dalton transactions. Volume 44:Issue 40(2015)
• Page Start: 17448
• Page End: 17452
• Publication Date: 2015-09-02
• Subjects: Chemistry, Inorganic -- Periodicals; Chemistry, Physical and theoretical -- Periodicals; Chemistry, Inorganic -- Periodicals; 546.05
• DOI: 10.1039/c5dt02207j
• Languages: English
• ISSNs: 1477-9226

Abstract

Abstract : Competition between vinylidene rearrangement/1, 1-insertion and 1, 2-alkyne insertion into the Ir–Ar bond of [Cp*Ir(ppy-F4 )] + was observed on reaction with diarylacetylenes. The former process afforded the 9-membered iridacycle via the subsequent 1, 4-Ir migration. Abstract : Competition between vinylidene rearrangement/1, 1-insertion and 1, 2-alkyne insertion into the Ir–Ar bond of [Cp*Ir(ppy-F4 )] + was observed on reaction with diarylacetylenes. The former process afforded the iridacycle2 via the subsequent 1, 4-Ir migration, whereas the latter led to the pyridoisoquinolinium complex4 . Detailed analysis revealed that4 isomerizes to2 by heating at 50 °C.